CN103441305A - Power and energy storage lithium-ion battery and preparation method thereof - Google Patents
Power and energy storage lithium-ion battery and preparation method thereof Download PDFInfo
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- 238000004146 energy storage Methods 0.000 title claims abstract description 48
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 64
- 229910021384 soft carbon Inorganic materials 0.000 claims abstract description 56
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 42
- 229910021385 hard carbon Inorganic materials 0.000 claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 29
- 239000010439 graphite Substances 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000007773 negative electrode material Substances 0.000 claims description 48
- 230000004888 barrier function Effects 0.000 claims description 31
- 239000007774 positive electrode material Substances 0.000 claims description 29
- 239000003792 electrolyte Substances 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 21
- 229910003002 lithium salt Inorganic materials 0.000 claims description 19
- 159000000002 lithium salts Chemical class 0.000 claims description 19
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- 230000002441 reversible effect Effects 0.000 claims description 7
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 5
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 5
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- 239000002253 acid Substances 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 4
- 238000005524 ceramic coating Methods 0.000 claims description 4
- 239000011247 coating layer Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
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- 239000012528 membrane Substances 0.000 claims description 4
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- 238000003475 lamination Methods 0.000 claims description 3
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 claims description 3
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 claims description 3
- XJYDIOOQMIRSSY-UHFFFAOYSA-N 1,3,2-dioxathiepane 2-oxide Chemical compound O=S1OCCCCO1 XJYDIOOQMIRSSY-UHFFFAOYSA-N 0.000 claims description 2
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- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 claims description 2
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- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a preparation method of a power and energy storage lithium-ion battery. A negative active substance of the power and energy storage lithium-ion battery comprises soft carbon, hard carbon, a mixed material of soft carbon and graphite and a mixed material of hard carbon and graphite. The designing method of the battery comprises the steps of designing the gram volume of the negative active substance as the primary lithium-embedding gram volume, designing the gram volume of the positive active substance as the primary lithium-removal gram volume, designing the ratio of the capacity of the positive electrode and the capacity of the negative electrode to be (1: 1) to (1.5: 1). By adopting the designing method, the capacity and comprehensive performance of the battery can be remarkably improved, and excellent lithium-embedding and lithium-removal capacity of the soft carbon material and the hard carbon material can be adequately exerted. Compared with the existing lithium battery technology, the prepared power lithium battery has long service life, high multiplying power, high safety performance and excellent low-temperature performance and can be widely applied to the fields such as electric tools, various portable devices, spaceflight, starting power supply and the like.
Description
Technical field
The present invention relates to the lithium ion battery field, particularly, the present invention relates to a kind of power and energy storage lithium ion battery and preparation method thereof.
Background technology
Along with the development of New Energy Industry, at present in power and energy-storage battery field, lithium ion battery has obtained development extremely rapidly as new forms of energy battery green, environmental protection.Along with the expansion of field of lithium battery application, energy density, high rate performance, cycle performance, high temperature performance and the security performance of battery are had higher requirement.
In existing lithium ion battery, the most widely used is to take the battery of graphite as the negative pole system, yet graphite is because its degree of graphitization is high, there is height-oriented layer structure, poor with existing organic electrolyte system compatibility, in the first charge-discharge process, lithium can occur and organic solvent embeds altogether, graphite linings expands peels off, burst apart and efflorescence between graphite granule, cause electrode structure destruction, charge-discharge performance poor.In addition, due to graphite in charge and discharge process, lithium ion must embed and deviate from along the border of graphite crystal, response area is little, and the lithium ion the evolving path is long, and it must form and decompose the carbon lithium compound and completes the embedding of lithium ion and deviate from, be not suitable for high rate charge-discharge, high temperature performance is poor, and very easily analyses lithium in the charge and discharge process of battery, causes the safety problem of battery.
Because soft carbon, hard carbon class negative material integral body present unordered microporosity structure, interlamellar spacing is greater than traditional graphite material, higher than graphite to the lithium current potential, this specific character makes it have the ability of quick storage lithium and de-lithium, and in charge and discharge process, impedance is less, and the electrokinetic cell that soft carbon, hard carbon are made thus has excellent cycle performance, high rate performance, good cryogenic property and excellent security performance.But the disordering structure that soft carbon, hard carbon are certain because its internal structure exists, cause its first efficiency lower than graphite type material, adopt Capacity design in existing battery preparation method, be that the positive and negative electrode active material adopts reversible specific capacity to carry out battery design, will cause cell integrated capacity low, excellent properties is difficult to performance.
Summary of the invention
For the deficiencies in the prior art, one of purpose of the present invention is to provide the preparation method of a kind of power and energy storage lithium ion battery, to improve performance, high rate charge-discharge performance, the security performance of power and energy storage lithium ion battery whole volume, low temperature charge-discharge performance and cycle performance.
The preparation method of described power and energy storage lithium ion battery comprises: according to following principle, prepare negative pole and positive pole: the negative electrode active material gram volume is its embedding lithium gram volume first, the positive active material gram volume is its de-lithium gram volume first, and the ratio of capacity of negative plates and positive electrode capacity is 1:1～1.5:1.
Preferably, the preparation method of described power and energy storage lithium ion battery comprises the following steps:
(1) adopt the negative electrode active material of 70～99.5wt%, the conductive agent of 0.2～28wt% and the binding agent of 0.2～28wt% to prepare cathode pole piece, and adopt the positive active material of 70～99.5wt%, the conductive agent of 0.2～28wt% and the binding agent of 0.2～28wt% to prepare anode pole piece; Wherein, described negative electrode active material gram volume is its embedding lithium gram volume first, and described positive active material gram volume is its de-lithium gram volume first, and the ratio of capacity of negative plates and positive electrode capacity is 1:1～1.5:1;
(2) positive plate and the negative plate that adopt step (1) to prepare prepare power and energy storage lithium ion battery.
Preferably, the preparation method of described power and energy storage lithium ion battery comprises the following steps:
(1) binding agent of the conductive agent of the negative electrode active material of 70～99.5wt%, 0.2～28wt% and 0.2～28wt% is mixed into to slurry, then the slurry mixed is coated in to the Copper Foil two sides uniformly, after baking, roll-in, soldering polar ear, makes cathode pole piece; The binding agent of the conductive agent of the positive active material of 70～99.5wt%, 0.2～28wt% and 0.2～28wt% is mixed into to uniform sizing material, then the slurry mixed is coated in to the aluminium foil two sides uniformly, after baking, roll-in, soldering polar ear, makes anode pole piece; Wherein, described negative electrode active material gram volume is its embedding lithium gram volume first, and described positive active material gram volume is its de-lithium gram volume first, and the ratio of capacity of negative plates and positive electrode capacity is 1:1～1.5:1;
(2) positive plate step (1) prepared and negative plate and barrier film form battery core in the mode of coiling or lamination, wherein between positive plate and negative plate, with barrier film, separate, and negative pole auxiliary material zone encases anodal auxiliary material zone fully; The shell of subsequently battery core being packed into, inject electrolyte, obtains battery, then it is standing, change into, partial volume, obtain power and energy storage lithium ion battery.
The ratio of described capacity of negative plates and positive electrode capacity can be, such as: 1.05:1,1.1:1,1.15:1,1.19:1,1.21:1,1.25:1,1.3:1,1.35:1,1.4:1 .45:1,1.47:1,1.48:1 or 1.49:1 etc., preferably 1:1～1.2:1.
Preferably, in described cathode size, the content of negative electrode active material is 75～99.2wt%, is particularly preferably 80～99wt%.
Preferably, in described cathode size, the content of conductive agent is 0.3～25wt%, is particularly preferably 0.5～15wt%.
Preferably, in described cathode size, the content of binding agent is 0.3～25wt%, is particularly preferably 0.5～15wt%.
Preferably, described negative electrode active material is soft carbon or hard carbon, or the mixture of soft carbon or hard carbon and graphite; Preferably, the average grain diameter (D of described soft carbon or hard carbon
50) be 0.1～40 μ m, specific area is 0.1～15.0m
2/ g, compacted density is 1.0～2.0g/cm
3, reversible capacity is 150～600mAh/g first, coulombic efficiency is greater than 70% first; Preferably, the average grain diameter (D of described soft carbon or hard carbon
50) be 0.3～35 μ m, be particularly preferably 0.5～30 μ m; Preferably, the specific area of described soft carbon or hard carbon is 0.3～10m
2/ g, be particularly preferably 0.5～8.0m
2/ g; Preferably, the compacted density of described soft carbon or hard carbon is 1.05～1.85g/cm
3, be particularly preferably 1.10～1.75g/cm
3; Preferably, the reversible capacity first of described soft carbon or hard carbon is 180～550mAh/g, is particularly preferably 200～500mAh/g; Preferably, the coulombic efficiency first of described soft carbon or hard carbon is greater than 75%, particularly preferably is greater than 78%; Preferably, the average grain diameter (D of described graphite
50) than the average grain diameter (D of described soft carbon or hard carbon
50) large 1～15 μ m, further preferably, the average grain diameter (D of described graphite
50) than the average grain diameter (D of described soft carbon or hard carbon
50) large 1.5～12 μ m, particularly preferably, the average grain diameter (D of described graphite
50) than the average grain diameter (D of described soft carbon or hard carbon
50) large 2～10 μ m; Preferably, in the mixture of described soft carbon or hard carbon and graphite, the content of soft carbon or hard carbon is 10～95wt%, such as 11wt%, 12wt%, 15wt%, 19wt%, 21wt%, 25wt%, 30wt%, 35wt%, 40wt%, 50wt%, 55wt%, 65wt%, 70wt%, 75wt%, 79wt%, 81wt%, 85wt%, 90wt%, 92wt%, 93wt% or 94wt% etc., more preferably 20～70wt%, be particularly preferably 30～50wt%.
Preferably, the transistion metal compound that described positive active material is lithium, be particularly preferably cobalt acid lithium, nickle cobalt lithium manganate, nickel cobalt lithium aluminate, lithium nickelate, LiMn2O4, rich lithium nickel manganese oxide, LiFePO4, lithium manganese phosphate, 1 kind or the combination of at least 2 kinds in phosphoric acid vanadium lithium or manganese silicate of lithium, the typical but non-limiting example of described combination comprises: the combination of cobalt acid lithium and lithium nickelate, the combination of LiMn2O4 and phosphoric acid vanadium lithium, nickle cobalt lithium manganate, the combination of nickel cobalt lithium aluminate and lithium nickelate, LiMn2O4, the combination of LiFePO4 and lithium manganese phosphate, cobalt acid lithium, nickle cobalt lithium manganate, the combination of phosphoric acid vanadium lithium and manganese silicate of lithium, nickel cobalt lithium aluminate, lithium nickelate, LiMn2O4, the combination of rich lithium nickel manganese oxide and LiFePO4 etc.
Preferably, described cathode pole piece surface density is 50～250g/m
2, 90～200g/m more preferably
2.
Preferably, described anode pole piece surface density is 150～550g/m
2, 200～400g/m more preferably
2.
Preferably, described conductive agent is a kind or the combination of at least 2 kinds in superconductive carbon black, carbon fiber, crystalline flake graphite, carbon nano-tube or Graphene.
Preferably, described binding agent is a kind or the combination of at least 2 kinds in polyvinylidene fluoride, polytetrafluoroethylene, butadiene-styrene rubber, sodium carboxymethylcellulose, carboxymethyl cellulose, polyvinyl alcohol, Viton or polyurethane.
Preferably, described barrier film is the individual layer that contains PP, PE, bilayer or three layers of composite diaphragm and ceramic coating layer barrier film thereof, nonwoven fabrics barrier film, in polyester film, cellulose membrane, polyimide film, polyamide membrane, spandex or the aramid fiber film of processing through coating a kind.
Preferably, the thickness of described barrier film is 8～50 μ m, and more preferably 10～40 μ m, be particularly preferably 16～35 μ m.
Preferably, the solvent of described electrolyte is a kind or the combination of at least 2 kinds in ethylene carbonate, methyl ethyl carbonate alkene ester, propene carbonate, diethyl carbonate, dimethyl carbonate, methyl propyl carbonate, carbonic acid first isopropyl ester, gamma-butyrolacton, butylene, dibutyl carbonate, carbonic acid first butyl ester or dipropyl carbonate.
Preferably, the lithium salts that described electrolyte contains 0.1～3mol/L, further the preferred lithium salinity is 0.3～2.5mol/L, particularly preferably lithium salt is 0.5～2mol/L; Preferably, described lithium salts is LiBOB, LiPF
6, LiClO
4, LiCF
3sO
3or LiAsF
6in a kind or the combination of at least 2 kinds.
Preferably, described electrolyte contains additive; Preferably, described additive is vinylene carbonate, propylene sulfite, vinylethylene carbonate, fluorinated ethylene carbonate, 1,3-propane sultone, cyclohexyl benzene, glycol sulfite, phthalic anhydride, butylene sulfite, N, 1 kind or the combination of at least 2 kinds in N'-dimethyl trifluoroacetamide, biphenyl, three (trimethyl silane) phosphate, gamma-butyrolacton, propene carbonate, Isosorbide-5-Nitrae-butane sultones, organosilan, crown ether, fluoro borate or fluoro borine; Preferably, the content of described additive in electrolyte is 0.1～30wt%, and more preferably 0.3～25wt%, be particularly preferably 0.5～20wt%.
Two of purpose of the present invention is to provide a kind of power and energy storage lithium ion battery, by the method for the invention, prepared by described power and energy storage lithium ion battery.
Preferably, the use voltage range of described power and energy storage lithium ion battery is (2.0～3.0V)～(3.6～4.8V), is particularly preferably (2.0～2.75V)～(3.8～4.6V).
Preferably, the serviceability temperature scope of described power and energy storage lithium ion battery is-60～80 ℃.
Compared with prior art, by the capacity matching design of battery, there is following beneficial effect in preparation method of the present invention:
(1) preparation method of the present invention can improve the performance of battery plus-negative plate active material gram volume significantly, more than gram volume lifting amplitude can reach 10～30mAh/g, make cell integrated capacity and first efficiency get a promotion, improved the energy density of power and energy-storage battery;
(2) lithium battery that preparation method of the present invention obtains has high rate charge-discharge characteristic and excellent cycle performance, 60C multiplying power discharging capacity is more than 88% of 1C discharge capacity, normal temperature 5C circulates 1000 weeks capability retentions more than 90%, meets power and energy-storage battery to power, fill the requirement of using with the long-life soon;
(3) the resulting lithium battery of the present invention has good charge-discharge performance under-60 ℃～80 ℃, be greater than 50%-40 ℃ of lower 1C discharge capacities,-10 ℃ of lower 2C 1000 weeks capability retentions that circulate are greater than 93%, meet that the wide temperature scope of application of power and energy-storage battery requires and extreme condition under battery charging and discharging;
(4) the resulting lithium battery of the present invention cathode pole piece expansion rate in circulation and multiplying power discharging process is less than 5%, cathode pole piece is not analysed lithium, and battery is indeformable, and overcharging resisting, mistake are put, there is good security feature, meet the requirement to security performance of power and energy-storage battery.
The accompanying drawing explanation
Fig. 1 is the stacked soft carbon power of 14Ah Soft Roll and the energy-storage battery charging and discharging curve that the embodiment of the present invention 1 makes;
Fig. 2 is that the stacked soft carbon power of 14Ah Soft Roll and the energy-storage battery normal temperature 5C that the embodiment of the present invention 1 makes charges and discharge cyclic curve, wherein cyclic curve 1 is electrolyte A, cyclic curve 2 is electrolyte B, and cyclic curve 3 is the cyclic curve 1 battery normal temperature shelf cyclic curve that circulation obtained again afterwards in 3 months;
The stacked soft carbon power of the 14Ah Soft Roll made that Fig. 3 is the embodiment of the present invention 1 and energy-storage battery normal temperature multiplying power cross-circulation curve, its moderate multiplying factor intersects and charges and discharge for 1C charges and discharge circulation 100 weeks, 5C that circulation 100 weeks, 10C charge and discharge circulation 100 weeks, 20C charges and discharge and circulates 100 weeks, 4 circulations hocket, finally with 1C, charge and discharge circulation 200 weeks, the global cycle number of times is 2000 times;
To be that the soft carbon power of cylinder 18650/1.5Ah and the energy-storage battery normal temperature 5C that the embodiment of the present invention 4 makes charges and discharge, 10C charges and discharge fill 20C with 5C to Fig. 4 puts cyclic curve;
Fig. 5 is the soft carbon power of cylinder 18650/1.5Ah and energy-storage battery-10 ℃ that the embodiment of the present invention 4 makes, and 1C charges and discharge with 2C and charges and discharge cyclic curve;
Fig. 6 is the soft carbon power of cylinder 18650/1.5Ah and the energy-storage battery multiplying power discharging curve that the embodiment of the present invention 4 makes;
Fig. 7 is that the soft carbon power of cylinder 18650/2.0Ah and the energy-storage battery normal temperature 5C that the embodiment of the present invention 7 makes charges and discharge cyclic curve.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment helps to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1
The battery size of preparation is P85120190/14Ah, and battery core adopts stacked, by aluminum plastic film, encapsulates and forms Soft Roll power and energy-storage lithium battery; The physical and chemical indexes of the soft carbon of described negative electrode active material is in Table 1.Anodal and negative electrode active material gram volume takes off lithium and embedding lithium gram volume design first first according to it respectively, and the design of both positive and negative polarity capacity matching is 108% design according to capacity of negative plates and positive electrode capacity ratio, and the specific design method is in Table 2.
(1) by the soft carbon of 94.5wt%, the carbon black of 2.0wt%, the carboxymethyl cellulose of 1.5wt%, butadiene-styrene rubber and the aqueous solvent of 2.0wt% are mixed into slurry, are coated in uniformly on Copper Foil, and coated face density is two-sided 140g/m
2, after baking, roll-in, soldering polar ear, make cathode pole piece.
(2) by the nickle cobalt lithium manganate of 94.5wt%, the carbon black of 4.0wt%, 1.5wt% polyvinylidene fluoride and solvent NMP are mixed into slurry, are coated in uniformly on aluminium foil, and coated face density is two-sided 230g/m
2, after baking, roll-in, soldering polar ear, make anode pole piece.
(3) preparation of battery core: the positive plate, negative plate and the barrier film that prepare are formed to battery core in the mode of lamination, wherein separate with barrier film between positive plate and negative plate, negative pole auxiliary material zone encases anodal auxiliary material zone fully.Barrier film adopts tri-layers of composite ceramics coat barrier film of PP/PE/PP that thickness is 35 μ m.Encapsulate and form soft pack cell by aluminum plastic film after the both positive and negative polarity lug is welded and fixed by large power supersonic.Subsequently battery core is put into to 85 ℃ of vacuum ovens and toasted, baking time is 24～36h, and below vacuum degree-0.08Mpa, removing in battery is moisture.
(4) inject a certain amount of electrolyte in the battery core after above-mentioned baking, standing after vacuum suction, sealing.Electrolyte is comprised of solvent, lithium salts and additive, and concrete composition is as follows:
Electrolyte A: ethylene carbonate, methyl ethyl carbonate alkene ester, dimethyl carbonate 10:35:55 in mass ratio are mixed into solvent, add 1 of 5% fluorinated ethylene carbonate, 5% propene carbonate, 1.5% vinylene carbonate and 1.0%, the 3-propane sultone, the LiPF that lithium salts is 1.35mol/L
6.
Electrolyte B: ethylene carbonate, methyl ethyl carbonate alkene ester, dimethyl carbonate, propene carbonate 15:35:40:10 in mass ratio are mixed into solvent, add 8% fluorinated ethylene carbonate, 1.5% vinylene carbonate, the LiPF that lithium salts is 1.20mol/L
6.
(5) above-mentioned battery changed into, obtain power and energy-storage lithium battery after aging and partial volume.
Through partial volume, more than the actual 1C capacity performance of battery 14.5Ah, more than the battery cell energy density reaches 150Wh/Kg, more than positive active material 1C gram volume performance 156mAh/g, more than negative electrode active material 1C gram volume performance 252mAh/g, first charge-discharge is efficiency more than 85% first.Normal temperature 1C charging and discharging curve as shown in Figure 1.
Then battery is carried out to normal temperature 5C and charge and discharge the cycle performance test, after tested, 1000 weeks rear capability retentions of this circulating battery are 90.5%, after the battery normal temperature shelf after test 3 months, again circulate 1000 weeks, the capacity attenuation degree is only 2.7%, and as shown in Figure 2, the capacity of shelving rear battery is initial capacity more than 95%.
For the switching between different multiplying in the actual use procedure of simulated battery discharges and recharges, by the battery of preparation at normal temperatures according to 1C charge and discharge the circulation 100 weeks, 5C charge and discharge the circulation 100 weeks, 10C charge and discharge the circulation 100 weeks, 20C charge and discharge the circulation 100 weeks, 4 circulations hocket, finally with 1C, charge and discharge circulation 200 weeks, 2000 capability retentions of global cycle test are more than 80%, as shown in Figure 3.
By battery, as for after shelving 8h under-40 ℃, with the 1C electric discharge, discharge capacity is greater than 50%; Subsequently by battery as for after shelving 6h under 60 ℃, with the 1C electric discharge, discharge capacity is greater than 98%;
Carry out 3C/12V after battery is completely charged and overcharge, battery is without on fire, blast, 38 ℃ of battery surface maximum temperatures.
It is 2.0～4.2V that above battery is used voltage range.
Comparative Examples 1
Adopt the method identical with embodiment 1 to prepare pole piece and battery, different is anodal and negative electrode active material is designed according to prior art, and gram volume is designed according to its reversible gram volume respectively, and the specific design method is in Table 2.Cathode pole piece coated face density is two-sided 140g/m
2, anode pole piece coated face density is two-sided 214g/m
2.
Through partial volume, the performance of the actual 1C capacity of battery be only the 13.0Ah left and right, and the performance of positive active material 1C gram volume is less than 140mAh/g, and negative electrode active material 1C gram volume is brought into play and is less than 230mAh/g, first charge-discharge first efficiency lower than 78%.
Battery is carried out to normal temperature 5C and charge and discharge the cycle performance test, after tested, 800 weeks rear capability retentions of this circulating battery are only 80.3%.
Adopt different gram volume methods for designing, the performance of battery actual capacity, the performance of both positive and negative polarity active material gram volume, cycle life are all lower than embodiment 1.
Embodiment 2
Adopt the method identical with embodiment 1 to prepare battery, different is that the design of both positive and negative polarity capacity matching is 100% design according to capacity of negative plates and positive electrode capacity ratio.
Through partial volume, more than the actual 1C capacity performance of battery 14.8Ah, more than the battery cell energy density reaches 150Wh/Kg, more than positive active material 1C gram volume performance 158mAh/g, more than negative electrode active material 1C gram volume performance 258mAh/g, first charge-discharge is efficiency more than 85% first.
Then battery is carried out to normal temperature 5C and charge and discharge the cycle performance test, after tested, 1000 weeks rear capability retentions of this circulating battery are 86.7%.
By battery, as for after shelving 8h under-40 ℃, with the 1C electric discharge, discharge capacity is greater than 53%.
Carry out 3C/12V after battery is completely charged and overcharge, battery is without on fire, blast, 46 ℃ of battery surface maximum temperatures.
It is 2.0～4.2V that above battery is used voltage range.
Embodiment 3
Adopt the method identical with embodiment 1 to prepare battery, different is that the design of both positive and negative polarity capacity matching is 150% design according to capacity of negative plates and positive electrode capacity ratio.
Through partial volume, more than the actual 1C capacity performance of battery 13.2Ah, more than positive active material 1C gram volume performance 142mAh/g, more than negative electrode active material 1C gram volume performance 237mAh/g, first charge-discharge is efficiency 81.6% first.
Then battery is carried out to normal temperature 5C and charge and discharge the cycle performance test, after tested, 1000 weeks rear capability retentions of this circulating battery are 84.7%.
Carry out 3C/12V after battery is completely charged and overcharge, battery is without on fire, blast, 42 ℃ of battery surface maximum temperatures.
It is 2.0～4.2V that above battery is used voltage range.
Embodiment 4
The battery size of preparation is cylinder 18650/1.5Ah, and battery core adopts takeup type, by the encapsulation of column type box hat, forms power and energy-storage lithium battery; The physical and chemical indexes of the soft carbon of described negative electrode active material is in Table 1.Anodal and negative electrode active material gram volume respectively according to its first de-lithium and first embedding lithium gram volume designed, the design of both positive and negative polarity capacity matching is 120% design according to capacity of negative plates and positive electrode capacity ratio, the specific design method is in Table 2.
(1) by the soft carbon of 94.5wt%, the carbon black of 2.0wt%, the carboxymethyl cellulose of 1.5wt%, butadiene-styrene rubber and the aqueous solvent of 2.0wt% are mixed into slurry, are coated in uniformly on Copper Foil, and coated face density is two-sided 132g/m
2, after baking, roll-in, soldering polar ear, make cathode pole piece.
(2) by the nickle cobalt lithium manganate of 94.5wt%, the carbon black of 4.0wt%, 1.5wt% polyvinylidene fluoride and solvent NMP are mixed into slurry, are coated in uniformly on aluminium foil, and coated face density is two-sided 210g/m
2, after baking, roll-in, soldering polar ear, make anode pole piece.
(3) preparation of battery core: the positive plate, negative plate and the barrier film that prepare are formed to battery core in the mode of reeling, wherein separate with barrier film between positive plate and negative plate, negative pole auxiliary material zone encases anodal auxiliary material zone fully.Barrier film adopts tri-layers of composite diaphragm of PP/PE/PP that thickness is 16 μ m.Battery after reeling is packed in 18650 box hats, and negative lug is fixed by resistance welded, and positive pole ear is fixed by laser welding, subsequently battery core being put into to 85 ℃ of vacuum ovens is toasted, baking time is 24～36h, and below vacuum degree-0.08Mpa, removing in battery is moisture.
(4) inject a certain amount of electrolyte in the battery core after above-mentioned baking, standing after vacuum suction, sealing.Electrolyte is comprised of solvent, lithium salts and additive, concrete composition is as follows: ethylene carbonate, methyl ethyl carbonate alkene ester, dimethyl carbonate 10:35:55 in mass ratio are mixed into solvent, add 1 of 5% fluorinated ethylene carbonate, 5% propene carbonate, 1.5% vinylene carbonate and 1.0%, the 3-propane sultone, the LiPF that lithium salts is 1.35mol/L
6.
(5) above-mentioned battery changed into, obtain power and energy-storage lithium battery after aging and partial volume.
Through partial volume, more than the actual 1C capacity of battery performance 1.5Ah, more than positive active material 1C gram volume performance 155mAh/g, more than negative electrode active material 1C gram volume performance 254mAh/g, first charge-discharge is efficiency more than 83% first.
The gained battery is carried out respectively to normal temperature 5C circulation, normal temperature 10C circulation, normal temperature 5C to be filled 20C and puts circulation and low temperature-10 ℃ 1C and 2C circulation, after 1000 weeks, the battery capacity conservation rate is respectively 93.0%, 87.7%, 86.8% and 93.2%, 91.4%, as shown in Figure 4, Figure 5.
The soft carbon electrokinetic cell of gained carried out to the different multiplying electric discharge, discharge-rate is made as 1C, 5C, 10C, the 15C, 20C, 30C, 40C, 50C, 60C, after tested simultaneously, battery has excellent high rate performance, at normal temperatures, the 60C discharge capacity is more than 88%, as shown in Figure 6 of 1C discharge capacity.
By battery, as for after shelving 8h under-40 ℃, with the 1C electric discharge, discharge capacity is greater than 55%.
Carry out 3C/12V after battery is completely charged and overcharge, battery is without on fire, blast, 42 ℃ of battery surface maximum temperatures.
It is 2.0～4.2V that above battery is used voltage range.
Embodiment 5
The battery size of preparation is cylinder 18650/1.3Ah, and battery core adopts takeup type, by the encapsulation of column type box hat, forms power and energy-storage lithium battery; The physical and chemical indexes of described negative electrode active material hard carbon is in Table 1.Anodal and negative electrode active material gram volume respectively according to its first de-lithium and first embedding lithium gram volume designed, the design of both positive and negative polarity capacity matching is 108% design according to capacity of negative plates and positive electrode capacity ratio, specifically the battery design method is in Table 2.
(1) by the hard carbon of 94.5wt%, the carbon black of 2.0wt%, the carboxymethyl cellulose of 1.5wt%, butadiene-styrene rubber and the aqueous solvent of 2.0wt% are mixed into slurry, are coated in uniformly on Copper Foil, and coated face density is two-sided 121g/m
2, after baking, roll-in, soldering polar ear, make cathode pole piece.
(2) by the layered lithium manganate of 94.5wt%, the carbon black of 4.0wt%, 1.5wt% polyvinylidene fluoride and solvent NMP are mixed into slurry, are coated in uniformly on aluminium foil, and coated face density is two-sided 232g/m
2, after baking, roll-in, soldering polar ear, make anode pole piece.
(3) preparation of battery core: the positive plate, negative plate and the barrier film that prepare are formed to battery core in the mode of reeling, wherein separate with barrier film between positive plate and negative plate, negative pole auxiliary material zone encases anodal auxiliary material zone fully.Barrier film adopts the PE+ ceramic coating layer composite diaphragm that thickness is 20 μ m.Battery after reeling is packed in 18650 box hats, and negative lug is fixed by resistance welded, and positive pole ear is fixed by laser welding, subsequently battery core being put into to 85 ℃ of vacuum ovens is toasted, baking time is 24～36h, and below vacuum degree-0.08Mpa, removing in battery is moisture.
(4) inject a certain amount of electrolyte in the battery core after above-mentioned baking, standing after vacuum suction, sealing.Electrolyte is comprised of solvent, lithium salts and additive, concrete composition is as follows: ethylene carbonate, methyl ethyl carbonate alkene ester, diethyl carbonate 20:40:40 in mass ratio are mixed into solvent, add 1 of 5% fluorinated ethylene carbonate, 8% propene carbonate, 1.5% vinylene carbonate and 1.0%, the 3-propane sultone, the LiPF that lithium salts is 1.25mol/L
6.
(5) above-mentioned battery changed into, obtain power and energy-storage lithium battery after aging and partial volume.
Through partial volume, more than the actual 1C capacity of battery performance 1.3Ah, more than positive active material 1C gram volume performance 128mAh/g, more than negative electrode active material 1C gram volume performance 248mAh/g, first charge-discharge is efficiency more than 81% first.
The gained battery is carried out respectively to normal temperature 10C and charge and discharge circulation, after 1000 weeks, the battery capacity conservation rate is more than 92%.
The soft carbon electrokinetic cell of gained carried out to the different multiplying electric discharge, discharge-rate is made as 1C, 5C, 10C, 20C, 30C, 40C, 60C simultaneously, and after tested, battery has excellent high rate performance, and at normal temperatures, the 60C discharge capacity is more than 90% of 1C discharge capacity.
It is 2.0～4.35V that above battery is used voltage range.
Embodiment 6
The battery size of preparation is cylinder 18650/1.5Ah, and battery core adopts takeup type, by the encapsulation of column type box hat, forms power and energy-storage lithium battery; The physical and chemical indexes of described negative electrode active material hard carbon is in Table 1.Anodal and negative electrode active material gram volume respectively according to its first de-lithium and first embedding lithium gram volume designed, the design of both positive and negative polarity capacity matching is 108% design according to capacity of negative plates and positive electrode capacity ratio, specifically the battery design method is in Table 2.
(1) by the hard carbon of 94.5wt%, the carbon black of 2.0wt%, the carboxymethyl cellulose of 1.5wt%, butadiene-styrene rubber and the aqueous solvent of 2.0wt% are mixed into slurry, are coated in uniformly on Copper Foil, and coated face density is two-sided 142.8g/m
2, after baking, roll-in, soldering polar ear, make cathode pole piece.
(2) by the layered lithium manganate of 94.5wt%, the carbon black of 4.0wt%, 1.5wt% polyvinylidene fluoride and solvent NMP are mixed into slurry, are coated in uniformly on aluminium foil, and coated face density is two-sided 200g/m
2, after baking, roll-in, soldering polar ear, make anode pole piece.
(3) preparation of battery core: the positive plate, negative plate and the barrier film that prepare are formed to battery core in the mode of reeling, wherein separate with barrier film between positive plate and negative plate, negative pole auxiliary material zone encases anodal auxiliary material zone fully.Barrier film adopts the PE+ ceramic coating layer composite diaphragm that thickness is 20 μ m.Battery after reeling is packed in 18650 box hats, and negative lug is fixed by resistance welded, and positive pole ear is fixed by laser welding, subsequently battery core being put into to 85 ℃ of vacuum ovens is toasted, baking time is 24～36h, and below vacuum degree-0.08Mpa, removing in battery is moisture.
(4) inject a certain amount of electrolyte in the battery core after above-mentioned baking, standing after vacuum suction, sealing.Electrolyte is comprised of solvent, lithium salts and additive, concrete composition is as follows: ethylene carbonate, methyl ethyl carbonate alkene ester, methyl butyrate 30:30:40 in mass ratio are mixed into solvent, add 2% fluorinated ethylene carbonate, 2% propene carbonate,, the LiPF that lithium salts is 1.10mol/L
6liBOB with 0.15mol/L.
(5) above-mentioned battery changed into, obtain power and energy-storage lithium battery after aging and partial volume.
Through partial volume, more than the actual 1C capacity of battery performance 1.5Ah, more than positive active material 1C gram volume performance 189mAh/g, more than negative electrode active material 1C gram volume performance 257mAh/g, first charge-discharge is efficiency more than 82% first.
The gained battery is carried out respectively to normal temperature 5C and charge and discharge circulation, after 1000 weeks, the battery capacity conservation rate is 91.7%.
The soft carbon electrokinetic cell of gained carried out to the different multiplying electric discharge, discharge-rate is made as 1C, 5C, 10C, 20C, 30C, 40C, 60C simultaneously, and after tested, battery has excellent high rate performance, and at normal temperatures, the 60C discharge capacity is more than 89% of 1C discharge capacity.Battery low temperature-40 ℃ lower discharge capacity is 52.6% of 25 ℃ of discharge capacities of normal temperature
It is 2.0～4.6V that above battery is used voltage range.
Embodiment 7
The battery size of preparation is cylinder 18650/2.0Ah, and battery core adopts takeup type, by the encapsulation of column type box hat, forms soft carbon power and energy-storage lithium battery; The physical and chemical indexes of the soft carbon of described negative electrode active material is in Table 1.Anodal and negative electrode active material gram volume respectively according to its first de-lithium and first embedding lithium gram volume designed, the design of both positive and negative polarity capacity matching is 110% design according to capacity of negative plates and positive electrode capacity ratio, specifically the battery design method is in Table 2.
(1) by the soft carbon of 94.5wt%, the carbon black of 2.0wt%, the carboxymethyl cellulose of 1.5wt%, butadiene-styrene rubber and the aqueous solvent of 2.0wt% are mixed into slurry, are coated in uniformly on Copper Foil, and coated face density is two-sided 105g/m
2, after baking, roll-in, soldering polar ear, make cathode pole piece.
(2) by the nickle cobalt lithium manganate of 94.5wt%, the carbon black of 4.0wt%, 1.5wt% polyvinylidene fluoride and solvent NMP are mixed into slurry, are coated in uniformly on aluminium foil, and coated face density is two-sided 268g/m
2, after baking, roll-in, soldering polar ear, make anode pole piece.
(3) preparation of battery core: the positive plate, negative plate and the barrier film that prepare are formed to battery core in the mode of reeling, wherein separate with barrier film between positive plate and negative plate, negative pole auxiliary material zone encases anodal auxiliary material zone fully.Barrier film adopts tri-layers of composite diaphragm of PP/PE/PP that thickness is 20 μ m.Battery after reeling is packed in 18650 box hats, and negative lug is fixed by resistance welded, and positive pole ear is fixed by laser welding, subsequently battery core being put into to 85 ℃ of vacuum ovens is toasted, baking time is 24～36h, and below vacuum degree-0.08Mpa, removing in battery is moisture.
(4) inject a certain amount of electrolyte in the battery core after above-mentioned baking, standing after vacuum suction, sealing.Electrolyte is comprised of solvent, lithium salts and additive, concrete composition is as follows: propene carbonate, ethylene carbonate, methyl ethyl carbonate alkene ester, dimethyl carbonate 5:25:45:25 in mass ratio are mixed into solvent, add 1 of 5% fluorinated ethylene carbonate, 1.5% vinylene carbonate and 1.0%, the 3-propane sultone, the LiPF that lithium salts is 1.20mol/L
6.
(5) above-mentioned battery changed into, obtain power and energy-storage lithium battery after aging and partial volume.
Through partial volume, more than the actual 1C capacity of battery performance 2.0Ah, more than positive active material 1C gram volume performance 152mAh/g, more than negative electrode active material 1C gram volume performance 403mAh/g, first charge-discharge is efficiency more than 81% first.
The gained battery is carried out respectively to normal temperature 5C and charge and discharge circulation, after 1000 weeks, the battery capacity conservation rate is 86.7%, as shown in Figure 7.
The soft carbon electrokinetic cell of gained carried out to the different multiplying electric discharge, discharge-rate is made as 1C, 5C, 10C, 20C, 30C, 40C simultaneously, and after tested, battery has excellent high rate performance, and at normal temperatures, the 40C discharge capacity is more than 88% of 1C discharge capacity.
It is 2.0～4.2V that above battery is used voltage range.
Comparative Examples 2
Adopt the method identical with embodiment 7 to prepare pole piece and battery, different is anodal and negative electrode active material is designed according to prior art, and gram volume is designed according to its reversible gram volume respectively, and cathode pole piece coated face density is two-sided 105g/m
2, anode pole piece coated face density is two-sided 246g/m
2.The specific design method is in Table 2.
Through partial volume, the performance of the actual 1C capacity of battery be only the 1.7Ah left and right, and the performance of positive active material 1C gram volume is 132mAh/g, and the performance of negative electrode active material 1C gram volume is 364mAh/g, first charge-discharge first efficiency lower than 76%.
The gained battery is carried out respectively to normal temperature 5C circulation, and after 800 weeks, the battery capacity conservation rate is less than 80%.
It is 2.0～4.2V that above battery is used voltage range.
Embodiment 8
The battery size of preparation is cylinder 18650/1.5Ah, and battery core adopts takeup type, by the encapsulation of column type box hat, forms soft carbon power and energy-storage lithium battery; The physical and chemical indexes of described negative electrode active material hard carbon is in Table lattice 1.Anodal and negative electrode active material gram volume respectively according to its first de-lithium and first embedding lithium gram volume designed, the design of both positive and negative polarity capacity matching is 105% design according to capacity of negative plates and positive electrode capacity ratio, the specific design method is in Table 2.
(1) by the hard carbon of 94.5wt%, the carbon black of 2.0wt%, the carboxymethyl cellulose of 1.5wt%, butadiene-styrene rubber and the aqueous solvent of 2.0wt% are mixed into slurry, are coated in uniformly on Copper Foil, and coated face density is two-sided 100g/m
2, after baking, roll-in, soldering polar ear, make cathode pole piece.
(2) by the LiFePO4 of 93.0wt%, the carbon black of 4.0wt%, 3.0wt% polyvinylidene fluoride and solvent NMP are mixed into slurry, are coated in uniformly on aluminium foil, and coated face density is two-sided 330g/m
2, after baking, roll-in, soldering polar ear, make anode pole piece.
(3) preparation of battery core: the positive plate, negative plate and the barrier film that prepare are formed to battery core in the mode of reeling, wherein separate with barrier film between positive plate and negative plate, negative pole auxiliary material zone encases anodal auxiliary material zone fully.Barrier film adopts tri-layers of composite diaphragm of PP/PE/PP that thickness is 20 μ m.Battery after reeling is packed in 18650 box hats, and negative lug is fixed by resistance welded, and positive pole ear is fixed by laser welding, subsequently battery core being put into to 85 ℃ of vacuum ovens is toasted, baking time is 24～36h, and below vacuum degree-0.08Mpa, removing in battery is moisture.
(4) inject a certain amount of electrolyte in the battery core after above-mentioned baking, standing after vacuum suction, sealing.Electrolyte is comprised of solvent, lithium salts and additive, concrete composition is as follows: ethylene carbonate, diethyl carbonate, dimethyl carbonate 20:30:40 in mass ratio are mixed into solvent, add 1 of 5% propene carbonate, 2.0% vinylene carbonate and 2.0%, the 3-propane sultone, the LiPF that lithium salts is 1.25mol/L
6.
(5) above-mentioned battery changed into, obtain power and energy-storage lithium battery after aging and partial volume.
Through partial volume, more than the actual 1C capacity of battery performance 1.5Ah, more than positive active material 1C gram volume performance 134mAh/g, more than negative electrode active material 1C gram volume performance 402mAh/g, first charge-discharge is efficiency more than 82% first.
The gained battery is carried out respectively to normal temperature 5C charges and discharge circulation, normal temperature 10C charges and discharge circulation, after 2000 weeks, the battery capacity conservation rate is respectively 94.6% and 91.8%.
The soft carbon electrokinetic cell of gained carried out to the different multiplying electric discharge simultaneously, discharge-rate is made as 1C, 5C, 10C, 15C, 20C, 30C, 40C, 50C, 60C, and after tested, battery has excellent high rate performance, at normal temperatures, the 60C discharge capacity is more than 94.8% of 1C discharge capacity.Low temperature-40 ℃ discharge capacity is 46.7% of 25 ℃ of discharge capacities of normal temperature.
It is 2.0～3.8V that above battery is used voltage range.
Embodiment 9
The battery size of preparation is P7090130/7.6Ah, adopt the method identical with embodiment 1 to prepare pole piece and battery, different is the mixture that negative electrode active material is soft carbon 30%+ graphite 70%, and the average grain diameter of soft carbon is identical with embodiment 7, the average grain diameter (D5 of graphite
0) be 16.384 μ m, negative electrode active material design gram volume is 433.5mAh/g, positive active material design gram volume is identical with embodiment 1; Cathode pole piece coated face density is 118g/m
2, compacted density is 1.55g/cm
3, anode pole piece coated face density is 276g/m
2.
Through partial volume, more than the actual 1C capacity performance of battery 7.72Ah, more than battery cell energy density 175Wh/Kg, more than positive active material 1C gram volume performance 148mAh/g, more than negative electrode active material 1C gram volume performance 345mAh/g, first charge-discharge is efficiency more than 84% first.
The gained battery is carried out to normal temperature 2C circulation, and after 1000 weeks, the battery capacity conservation rate is more than 85%, and 800 weeks rear capability retentions of the graphite cathode circulating battery of similar contrast are lower than 80%.The 10C discharge capacity is 93.4% of 0.5C discharge capacity.Low temperature-20 ℃ discharge capacity is more than 83% of 25 ℃ of discharge capacities of normal temperature.
It is 2.0～4.2V that above battery is used voltage range, and it is 3.0～4.2V that the graphite material battery is used voltage range.
Embodiment 10
The battery size of preparation is P7090130/7.6Ah, adopt the method identical with embodiment 9 to prepare pole piece and battery, different is the mixture that negative electrode active material is soft carbon 50%+ graphite 50%, the average grain diameter of soft carbon and graphite is identical with embodiment 9, negative electrode active material design gram volume is 438mAh/g, and positive active material design gram volume is identical with embodiment 9; Cathode pole piece coated face density is 117g/m
2, compacted density is 1.45g/cm
3, anode pole piece coated face density is 306g/m
2.
Through partial volume, more than the actual 1C capacity performance of battery 7.68Ah, more than battery cell energy density 168Wh/Kg, more than positive active material 1C gram volume performance 150mAh/g, more than negative electrode active material 1C gram volume performance 356mAh/g, first charge-discharge is efficiency more than 82% first.
The gained battery is carried out to normal temperature 2C circulation, and after 1600 weeks, the battery capacity conservation rate is more than 82%.The 10C discharge capacity is 94.6% of 0.5C discharge capacity.Low temperature-20 ℃ discharge capacity is more than 87% of 25 ℃ of discharge capacities of normal temperature.
It is 2.0～4.2V that above battery is used voltage range.
Embodiment 11
The battery size of preparation is P7090130/7.6Ah, adopt the method identical with embodiment 9 to prepare pole piece and battery, different is the mixture that negative electrode active material is hard carbon 30%+ graphite 70%, the average grain diameter of hard carbon is identical with embodiment 8, the average grain diameter of graphite is identical with embodiment 9, negative electrode active material design gram volume is 434mAh/g, and positive active material design gram volume is identical with embodiment 9; Cathode pole piece coated face density is 119g/m
2, compacted density is 1.55g/cm
3, anode pole piece coated face density is 305g/m
2.
Battery actual capacity performance is 7.65Ah, and more than positive active material 1C gram volume performance 147mAh/g, more than negative electrode active material 1C gram volume performance 348mAh/g, first charge-discharge is efficiency more than 80% first.
The gained battery is carried out to normal temperature 2C circulation, and after 1500 weeks, the battery capacity conservation rate is more than 80%.The 10C discharge capacity is 96.2% of 0.5C discharge capacity.Low temperature-20 ℃ discharge capacity is more than 85% of 25 ℃ of discharge capacities of normal temperature.
It is 2.0～4.2V that above battery is used voltage range.
Table 1
Table 2
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.The person of ordinary skill in the field should understand, any improvement in the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and auxiliary element, the selection of concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (10)
1. the preparation method of a power and energy storage lithium ion battery, comprise: according to following principle, prepare negative pole and positive pole: the negative electrode active material gram volume is its embedding lithium gram volume first, the positive active material gram volume is its de-lithium gram volume first, and the ratio of capacity of negative plates and positive electrode capacity is 1:1～1.5:1.
2. the method for claim 1, is characterized in that, described comprising the following steps:
(1) adopt the negative electrode active material of 70～99.5wt%, the conductive agent of 0.2～28wt% and the binding agent of 0.2～28wt% to prepare cathode pole piece, and adopt the positive active material of 70～99.5wt%, the conductive agent of 0.2～28wt% and the binding agent of 0.2～28wt% to prepare anode pole piece; Wherein, described negative electrode active material gram volume is its embedding lithium gram volume first, and described positive active material gram volume is its de-lithium gram volume first, and the ratio of capacity of negative plates and positive electrode capacity is 1:1～1.5:1;
(2) positive plate and the negative plate that adopt step (1) to prepare prepare power and energy storage lithium ion battery.
3. method as claimed in claim 1 or 2, is characterized in that, described comprising the following steps:
(1) binding agent of the conductive agent of the negative electrode active material of 70～99.5wt%, 0.2～28wt% and 0.2～28wt% is mixed into to slurry, then the slurry mixed is coated in to the Copper Foil two sides uniformly, after baking, roll-in, soldering polar ear, makes cathode pole piece; The binding agent of the conductive agent of the positive active material of 70～99.5wt%, 0.2～28wt% and 0.2～28wt% is mixed into to uniform sizing material, then the slurry mixed is coated in to the aluminium foil two sides uniformly, after baking, roll-in, soldering polar ear, makes anode pole piece; Wherein, described negative electrode active material gram volume is its embedding lithium gram volume first, and described positive active material gram volume is its de-lithium gram volume first, and the ratio of capacity of negative plates and positive electrode capacity is 1:1～1.5:1;
(2) positive plate step (1) prepared and negative plate and barrier film form battery core in the mode of coiling or lamination, wherein between positive plate and negative plate, with barrier film, separate, and negative pole auxiliary material zone encases anodal auxiliary material zone fully; The shell of subsequently battery core being packed into, inject electrolyte, obtains battery, then it is standing, change into, partial volume, obtain power and energy storage lithium ion battery.
4. as the described method of claim 1-3 any one, it is characterized in that, the ratio of described capacity of negative plates and positive electrode capacity is 1:1～1.2:1;
Preferably, in described cathode size, the content of negative electrode active material is 75～99.2wt%, is particularly preferably 80～99wt%;
Preferably, in described cathode size, the content of conductive agent is 0.3～25wt%, is particularly preferably 0.5～15wt%;
Preferably, in described cathode size, the content of binding agent is 0.3～25wt%, is particularly preferably 0.5～15wt%.
5. as the described method of claim 1-4 any one, it is characterized in that, described negative electrode active material is soft carbon or hard carbon, or the mixture of soft carbon or hard carbon and graphite;
Preferably, the average grain diameter of described soft carbon or hard carbon is 0.1～40 μ m, and specific area is 0.1～15.0m
2/ g, compacted density is 1.0～2.0g/cm
3, reversible capacity is 150～600mAh/g first, coulombic efficiency is greater than 70% first;
Preferably, the average grain diameter of described soft carbon or hard carbon is 0.3～35 μ m, is particularly preferably 0.5～30 μ m;
Preferably, the specific area of described soft carbon or hard carbon is 0.3～10m
2/ g, be particularly preferably 0.5～8.0m
2/ g;
Preferably, the compacted density of described soft carbon or hard carbon is 1.05～1.85g/cm
3, be particularly preferably 1.10～1.75g/cm
3;
Preferably, the reversible capacity first of described soft carbon or hard carbon is 180～550mAh/g, is particularly preferably 200～500mAh/g;
Preferably, the coulombic efficiency first of described soft carbon or hard carbon is greater than 75%, particularly preferably is greater than 78%;
Preferably, the average grain diameter of described graphite is than large 1～15 μ m of the average grain diameter of described soft carbon or hard carbon, further preferably, the average grain diameter of described graphite is than large 1.5～12 μ m of the average grain diameter of described soft carbon or hard carbon, particularly preferably, the average grain diameter of described graphite is than large 2～10 μ m of the average grain diameter of described soft carbon or hard carbon;
Preferably, in the mixture of described soft carbon or hard carbon and graphite, the content of soft carbon or hard carbon is 10～95wt%, and more preferably 20～70wt%, be particularly preferably 30～50wt%;
Preferably, the transistion metal compound that described positive active material is lithium, be particularly preferably a kind or the combination of at least 2 kinds in cobalt acid lithium, nickle cobalt lithium manganate, nickel cobalt lithium aluminate, lithium nickelate, LiMn2O4, rich lithium nickel manganese oxide, LiFePO4, lithium manganese phosphate, phosphoric acid vanadium lithium or manganese silicate of lithium.
6. as the described method of claim 2-5 any one, it is characterized in that, described cathode pole piece surface density is 50～250g/m
2, 90～200g/m more preferably
2;
Preferably, described anode pole piece surface density is 150～550g/m
2, 200～400g/m more preferably
2;
Preferably, described conductive agent is a kind or the combination of at least 2 kinds in superconductive carbon black, carbon fiber, crystalline flake graphite, carbon nano-tube or Graphene;
Preferably, described binding agent is a kind or the combination of at least 2 kinds in polyvinylidene fluoride, polytetrafluoroethylene, butadiene-styrene rubber, sodium carboxymethylcellulose, carboxymethyl cellulose, polyvinyl alcohol, Viton or polyurethane.
7. as the described method of claim 3-6 any one, it is characterized in that, described barrier film is the individual layer that contains PP, PE, bilayer or three layers of composite diaphragm and ceramic coating layer barrier film thereof, the nonwoven fabrics barrier film, in polyester film, cellulose membrane, polyimide film, polyamide membrane, spandex or aramid fiber film that coating is processed a kind;
Preferably, the thickness of described barrier film is 8～50 μ m, and more preferably 10～40 μ m, be particularly preferably 16～35 μ m;
Preferably, the solvent of described electrolyte is a kind or the combination of at least 2 kinds in ethylene carbonate, methyl ethyl carbonate alkene ester, propene carbonate, diethyl carbonate, dimethyl carbonate, methyl propyl carbonate, carbonic acid first isopropyl ester, gamma-butyrolacton, butylene, dibutyl carbonate, carbonic acid first butyl ester or dipropyl carbonate.
8. as the described method of claim 3-7 any one, it is characterized in that, the lithium salts that described electrolyte contains 0.1～3mol/L, further the preferred lithium salinity is 0.3～2.5mol/L, particularly preferably lithium salt is 0.5～2mol/L; Preferably, described lithium salts is LiBOB, LiPF
6, LiClO
4, LiCF
3sO
3or LiAsF
6in a kind or the combination of at least 2 kinds;
Preferably, described electrolyte contains additive; Preferably, described additive is vinylene carbonate, propylene sulfite, vinylethylene carbonate, fluorinated ethylene carbonate, 1,3-propane sultone, cyclohexyl benzene, glycol sulfite, phthalic anhydride, butylene sulfite, N, 1 kind or the combination of at least 2 kinds in N'-dimethyl trifluoroacetamide, biphenyl, three (trimethyl silane) phosphate, gamma-butyrolacton, propene carbonate, Isosorbide-5-Nitrae-butane sultones, organosilan, crown ether, fluoro borate or fluoro borine; Preferably, the content of described additive in electrolyte is 0.1～30wt%, and more preferably 0.3～25wt%, be particularly preferably 0.5～20wt%.
9. a power and energy storage lithium ion battery, is characterized in that, described power and energy storage lithium ion battery are by the described method preparation of claim 1-8 any one.
10. power as claimed in claim 9 and energy storage lithium ion battery, it is characterized in that, the use voltage range of described power and energy storage lithium ion battery is (2.0～3.0V)～(3.6～4.8V), is particularly preferably (2.0～2.75V)～(3.8～4.6V);
Preferably, the serviceability temperature scope of described power and energy storage lithium ion battery is-60～80 ℃.
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