CN110783529B - Lithium metal cathode for secondary battery and preparation and application thereof - Google Patents
Lithium metal cathode for secondary battery and preparation and application thereof Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 148
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 103
- 150000001622 bismuth compounds Chemical class 0.000 claims abstract description 43
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
- 239000002184 metal Substances 0.000 claims abstract description 41
- JYPVGDJNZGAXBB-UHFFFAOYSA-N bismuth lithium Chemical compound [Li].[Bi] JYPVGDJNZGAXBB-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910001152 Bi alloy Inorganic materials 0.000 claims abstract description 35
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 239000011230 binding agent Substances 0.000 claims abstract description 12
- 150000002642 lithium compounds Chemical class 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000006258 conductive agent Substances 0.000 claims abstract description 9
- 239000002002 slurry Substances 0.000 claims description 27
- -1 bismuth nitride Chemical class 0.000 claims description 15
- BRCWHGIUHLWZBK-UHFFFAOYSA-K bismuth;trifluoride Chemical compound F[Bi](F)F BRCWHGIUHLWZBK-UHFFFAOYSA-K 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims description 2
- 210000001787 dendrite Anatomy 0.000 abstract description 8
- 239000007773 negative electrode material Substances 0.000 abstract description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 34
- 239000011889 copper foil Substances 0.000 description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 21
- 238000000034 method Methods 0.000 description 18
- 239000013543 active substance Substances 0.000 description 17
- 239000000758 substrate Substances 0.000 description 14
- 239000006230 acetylene black Substances 0.000 description 13
- 210000004027 cell Anatomy 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- 229910012330 Li3Bi Inorganic materials 0.000 description 10
- 229910013107 LiBi Inorganic materials 0.000 description 10
- 239000002033 PVDF binder Substances 0.000 description 9
- 229910000416 bismuth oxide Inorganic materials 0.000 description 9
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 9
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000000151 deposition Methods 0.000 description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004070 electrodeposition Methods 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 230000008021 deposition Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229910001216 Li2S Inorganic materials 0.000 description 5
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 5
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical group [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- RGKSCFKZOUGILU-UHFFFAOYSA-N [Bi](=S)=S Chemical compound [Bi](=S)=S RGKSCFKZOUGILU-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/045—Electrochemical coating; Electrochemical impregnation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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
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- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
本发明属于锂二次电池负极材料领域，具体公开了一种二次电池用金属锂负极，包括集流体，复合在集流体上的锂铋合金基底层，以及复合在锂铋合金基底层表面的锂化合物层。本发明还公开了所述的二次电池用金属锂负极的制备方法，将铋的化合物、导电剂和粘结剂浆化后复合在集流体表面，随后再将复合在集流体上的铋的化合物和金属锂反应，制得所述的二次电池用金属锂负极。本发明独创性地发现，通过所述铋的化合物与金属锂的化学反应，生成有效的锂铋合金；促使金属锂在铋骨架中均匀生长，同时生产有效的SEI膜，保护金属锂，避免锂枝晶产生，从而提高金属锂负极的充放电库伦效率及循环寿命。The invention belongs to the field of negative electrode materials for lithium secondary batteries, and specifically discloses a metal lithium negative electrode for secondary batteries, comprising a current collector, a lithium-bismuth alloy base layer compounded on the current collector, and a lithium-bismuth alloy base layer compounded on the surface of the lithium-bismuth alloy base layer. Lithium compound layer. The invention also discloses the preparation method of the metal lithium negative electrode for secondary battery. The bismuth compound, the conductive agent and the binder are slurried and compounded on the surface of the current collector, and then the bismuth compound compounded on the current collector is compounded on the surface of the current collector. The compound reacts with metallic lithium to prepare the metallic lithium negative electrode for secondary battery. The invention creatively finds that through the chemical reaction of the bismuth compound and metal lithium, an effective lithium-bismuth alloy is formed; the metal lithium is promoted to grow uniformly in the bismuth framework, and an effective SEI film is produced at the same time to protect the metal lithium and avoid lithium Dendrites are generated, thereby improving the charge-discharge coulombic efficiency and cycle life of the lithium metal anode.
Description
Technical Field
The invention belongs to the field of new energy devices, and particularly relates to a novel metal lithium cathode for a secondary battery.
Background
With the rise of new energy fields, battery materials are receiving more and more attention. Metallic lithium relies on a high theoretical specific capacity (3860mAh/g), a lowest electrode potential (-3.040V vs. SHE), and a low density (0.53 g/cm)3) The lithium ion battery is an ideal negative electrode material in a lithium battery. However, lithium dendrites grow toAnd the potential safety hazard caused by the potential safety hazard limit the application of commercialization. Because the activity of the metal lithium is high, lithium dendrite grows in the charge-discharge cycle process, the battery short circuit and the coulombic efficiency are low, and the application of the metal lithium is restricted. The main effective methods at present are: modification of electrolyte, application of 3D current collectors, solid electrolyte applications, artificial SEI films, and the like.
For example: yang et al also realize good lithium storage performance by preparing porous copper through dealloying Cu-Zn alloy as a 3D current collector, but only improve the specific surface area, so that more metal lithium is exposed in the electrolyte without the protection of an SEI film, and the excellent performance of a lithium cathode is not enough to be realized [1 ]. Also the design of artificial SEI films is as follows: y Cao et Al uniformly coat Al2O3 on the surface of the lithium metal by a molecular deposition technology, effectively protect the lithium metal and inhibit the growth of lithium dendrites, but the artificial SEI film has large internal resistance and more side reactions, so that the coulombic efficiency of the battery cannot be improved.
[1]YANG C-P，YIN Y-X，ZHANG S-F，et al.Accommodating lithium into 3D current collectors with a submicron skeleton towards long-life lithium metal anodes[J].2015，6(8058)
[2]CaoY，Meng X，Elam JW.Atomic Layer Deposition of LixAlyS Solid-State Electrolytes for Stabilizing Lithium-Metal Anodes[J].Chemelectrochem，2016，3(6)：858-863.
Disclosure of Invention
In order to solve the technical defects of the conventional lithium negative electrode, the invention starts from an alloyed lithium metal negative electrode, modifies the lithium metal negative electrode, and keeps long cycle and high coulombic efficiency.
The second purpose of the invention is to provide a preparation method of the negative electrode.
The third purpose of the invention is to provide the application of the lithium metal negative electrode.
A lithium metal negative electrode for a secondary battery (also referred to as a lithium metal negative electrode for short in the invention) comprises a current collector, a lithium bismuth alloy substrate layer compounded on the current collector, and a lithium compound layer compounded on the surface of the lithium bismuth alloy substrate layer.
The lithium bismuth alloy is innovatively adopted as the substrate, the lithium compound layer is compounded on the substrate, the lithium metal negative electrode with the components and the structure can promote the uniform growth of the lithium metal in the bismuth framework, and is beneficial to avoiding the generation of lithium dendrites, meanwhile, an in-situ SEI film generated on the surface of the lithium bismuth alloy can stably exist in the electrolyte, the contact between the lithium metal negative electrode and the electrolyte is blocked, the occurrence of side reactions is effectively reduced, and therefore the charging and discharging coulomb efficiency and the cycle life of the lithium metal negative electrode are improved.
Preferably, the material of the lithium bismuth alloy substrate layer is Li3Bi and/or LiBi.
Preferably, the lithium compound layer is at least one of an oxide, a sulfide, a chloride, a nitride, a phosphide and a fluoride of lithium.
More preferably, the lithium compound layer is Li2O、LiCl、Li2S、Li3N、Li3P, LiF.
The current collector is a metal current collector, preferably at least one of copper, stainless steel, nickel and titanium.
Preferably, the thickness of the current collector is 10 to 20 micrometers, and more preferably 15 micrometers.
Preferably, the thickness of the lithium bismuth alloy substrate layer is 5 micrometers to 40 micrometers. Preferably, the thickness of the lithium compound layer is 5 nm to 500 nm.
The lithium metal negative electrode for a secondary battery further contains additional components, such as a conductive agent, a binder, and the like, which are allowable to be added to conventional lithium metal negative electrodes. The conductive agent can be compounded in the lithium bismuth alloy substrate layer.
The lithium metal negative electrode for the secondary battery comprises a current collector and an active substance compounded on the current collector, wherein the active substance is a reaction product of a bismuth compound and lithium metal; among them, the compound of bismuth is preferably bismuth (Bi) trioxide2O3) Trichlorination ofBismuth (BiCl)3) Bismuth trisulfide (Bi)2S3) Bismuth disulfide (BiS)2) Bismuth phosphide (Bi)3P), bismuth fluoride (BiF), bismuth nitride (Bi)3N).
Another innovation of the present invention is to provide a method for preparing a lithium bismuth alloy substrate in one step and in-situ compounding the lithium compound layer on the substrate. The preparation method of the metal lithium negative electrode for the secondary battery comprises the steps of slurrying a bismuth compound, a conductive agent and a binder, then compounding the slurried bismuth compound, the conductive agent and the binder on the surface of a current collector, and then reacting the bismuth compound compounded on the current collector with metal lithium to prepare the metal lithium negative electrode for the secondary battery.
According to the preparation method, a bismuth compound is adopted as an active ingredient, the bismuth compound is coated on a current collector in advance, then the bismuth compound and metal lithium are subjected to alloying reaction, and a lithium compound compounded on the alloy is formed in situ.
The conductive agent and the binder may employ additive components known in the art that may be used for a lithium metal negative electrode.
Preferably, the conductive agent is at least one of acetylene black, carbon fiber cloth, graphite, activated carbon, graphene, acetylene black, carbon nanotubes and ketjen black.
The binder is for example PVDF.
In the present invention, the conductive agent, the binder and the bismuth compound may be slurried with a solvent and then combined with the current collector by a conventional method, which may be a method well known in the art such as coating.
In the slurry, the proportion of the bismuth compound, the conductive carbon and the binder can be adjusted according to the requirement.
Preferably, in the slurry, the mass ratio of the bismuth compound, the conductive carbon and the binder is 10: 1.
Preferably, the coating thickness of the slurry after slurrying is 1-300 μm; preferably: 20 to 50 μm.
The bismuth compound is powdery, and the particle size of the bismuth compound is about 50-800 nm, preferably 50-300 nm. At the preferred particle size, it is helpful to produce a metallic lithium negative electrode having excellent properties, and it has been found that when the particle size of the bismuth compound is large (for example, larger than the upper limit required in the present invention), the bismuth compound does not sufficiently react with the metallic lithium; however, if the particles are small (for example, smaller than the lower limit required in the present invention), the binding force of the lithium bismuth alloy particles formed after the reaction is small, and the particles are easily pulverized.
Preferably, the bismuth compound is at least one of an oxide, a chloride, a sulfide, a bismuth phosphide, a bismuth fluoride and a bismuth nitride of bismuth.
Further preferably, the bismuth compound is at least one of bismuth trioxide, bismuth trichloride, bismuth trisulfide, bismuth disulfide, bismuth phosphide, bismuth fluoride and bismuth nitride; preferably at least one of bismuth trioxide, bismuth phosphide, bismuth trichloride and bismuth nitride.
More preferably, the bismuth compound is a mixture of bismuth fluoride and bismuth nitride. The invention further innovatively discovers that bismuth fluoride and bismuth nitride have excellent synergistic effect, and the combined use can unexpectedly and obviously improve the electrical property and the cycling stability.
Preferably, the bismuth compound is a mixture of bismuth fluoride and bismuth nitride in a mass ratio of 1-3: 1-3.
Preferably, the mass of the bismuth compound on the current collector is: 1mg/cm2～6mg/cm2To (c) to (d); prior to 3mg/cm2～5mg/cm2。
The method comprises the steps of uniformly mixing slurry of bismuth compounds, conductive carbon and a binder, coating the slurry on the surface of a current collector, drying the slurry, and filling metal lithium on the surface of the slurry to fully react the metal lithium with the bismuth compounds; the method for filling metallic lithium may be an existing method.
Preferably, the current collector combined with the bismuth compound is subjected to electrodeposition and/or lithium metal filling, and the lithium metal is reacted with the bismuth compound.
Preferably, the metallic lithium is filled into the bismuth compound current collector by electrodeposition. Compared with other methods for filling lithium, the method adopts electrochemical deposition, the lithium metal and bismuth compound are fully reacted, the reaction uniformity is better, the generated lithium bismuth alloy has strong binding force and high stability, and the surface is provided with an in-situ SEI film which can effectively protect the lithium bismuth alloy. The invention discovers that the performance of the prepared lithium metal negative electrode is further improved by innovatively adopting an electrodeposition method, for example, the cycle performance of the negative electrode is further improved.
By supplying metallic lithium to a current collector compounded with a bismuth compound, an alloying reaction proceeds, the reaction mechanism being, for example:
Bi+Li＝LiBi+Li3Bi
Bi2O3+Li＝LiBi+Li3Bi+Li2O
BiCl3+Li＝LiBi+Li3Bi+LiCl
Bi2S3+Li＝LiBi+Li3Bi+Li2S
BiS2+Li＝LiBi+Li3Bi+Li2S
Bi3P+Li＝LiBi+Li3Bi+Li3P
BiF+Li＝LiBi+Li3Bi+LiF
Bi3N+Li＝LiBi+Li3Bi+Li3N
the dosage of the metallic lithium is not less than 80 percent of the theoretical molar ratio of the bismuth compound for complete reaction.
In the lithium metal negative electrode, the content of the filled lithium metal is not less than the lithium amount lost in the first charge and discharge.
Preferably, the method comprises the following steps: in the lithium metal negative electrode, the content of the lithium metal is 1 mAh-8 mAh.
The invention also discloses a lithium metal cathode prepared by the preparation method. The metallic lithium negative electrode comprises a current collector, a lithium bismuth alloy substrate layer compounded on the current collector, andand the lithium compound layer is compounded on the surface of the lithium bismuth alloy substrate layer. The material of the lithium bismuth alloy substrate layer is Li3Bi and/or LiBi. The lithium compound layer is at least one of lithium oxide, sulfide, chloride, nitride, phosphide and fluoride; preferably Li2O、LiCl、Li2S、Li3N、Li3P, LiF.
The invention also provides application of the metal lithium cathode, and the metal lithium cathode is used as a cathode to be assembled into a lithium ion battery, a lithium sulfur battery or a lithium air battery.
Preferably, the lithium metal negative electrode is used for assembling a button lithium ion battery.
In the invention, the bismuth compound can generate a stable lithium bismuth alloy with the lithium metal, so that the stability of the lithium metal is improved, the lithium metal is promoted to be stably deposited in the lithium bismuth alloy, the generation of lithium dendrite is avoided, and the cycling stability and the coulombic efficiency of the lithium cathode taking the lithium bismuth alloy as a framework are further improved. And a lithium compound (Li) formed by a chemical reaction between metallic lithium and a bismuth compound2O、LiCl、Li2S、Li3P、LiF、Li3N) is an effective SEI film, the surface of the lithium bismuth alloy can be stabilized, the side reaction of the cathode and the electrolyte is inhibited, the metal lithium cathode is protected, and the cycle stability of the cathode is obviously improved.
The invention takes a bismuth compound as a substrate, and metal lithium deposited on the bismuth compound reacts with the bismuth compound through an electrochemical method to generate an effective lithium bismuth compound and a corresponding SEI film. Lithium bismuth is used as a current collector, and the surface of the lithium bismuth is effectively protected by an SEI film, so that the lithium metal cathode with high coulombic efficiency, long cycle and high capacity density is realized.
Has the advantages that:
the chemical reaction of the bismuth compound and the lithium is applied to generate a stable lithium bismuth alloy and a corresponding lithium-containing compound, wherein the lithium bismuth alloy can be used as a lithium deposition site, the lithium can be uniformly deposited on the lithium deposition site, the lithium-containing compound can be used as an SEI film effectively generated to separate the lithium from an electrolyte, the occurrence of side reactions is reduced, the double protection of the lithium deposition site and the SEI film is integrated, lithium dendrite generated by the nonuniform deposition of the lithium can be effectively avoided, and the high specific capacity characteristic of the lithium metal cathode in the charging and discharging process is maintained. The lithium secondary battery can effectively prevent the growth of lithium dendrites for a long time, and further improves the coulombic efficiency and the cycle life of the lithium secondary battery.
The invention innovatively adopts the preparation method, and can prepare the metallic lithium cathode in one step, and the inventor innovatively discovers that the electrical property of the metallic lithium cathode can be obviously prepared by adopting an electrodeposition method in the whole scheme of the invention.
Under the preparation method, the invention also innovatively discovers that the electrical property of the prepared lithium metal cathode can be further improved by combining bismuth fluoride and bismuth nitride.
Researches show that compared with the conventional metal lithium cathode, the cycle life of the cathode is prolonged by more than 3 times; compared with the cathode of the lithium bismuth alloy, the cycle performance is improved by nearly 2 times.
Drawings
FIG. 1 is an SEM photograph of metallic bismuth used in example 1;
FIG. 2 shows the metal bismuth and acetylene black used in example 1 smeared with a binder in a mass ratio of 8: 1 at a current density of 1mA/cm2And the area capacity is 1mAh/cm2Electrochemical performance of the copper foil under cycling is compared.
FIG. 3 shows bismuth trioxide (Bi) used in example 22O3) SEM picture of (1);
FIG. 4 shows bismuth trioxide (Bi) used in example 22O3) Smearing with acetylene black and adhesive in the mass ratio of 8: 1, and then coating at the current density of 1mA/em2And the area capacity is 1mAh/cm2Electrochemical performance of the copper foil under cycling is shown.
FIG. 5 shows bismuth trichloride (BiCl) used in example 33) Smearing with acetylene black and adhesive in the mass ratio of 8: 1, and then coating at the current density of 1mA/em2And the area capacity is 1mAh/cm2Electrochemical performance of the copper foil under cycling is shown.
FIG. 6 is a graph of the full cell electrochemical performance used in example 4;
FIG. 7 is a graph of the electrochemical performance of the half cell used in example 5;
FIG. 8 is a graph of the electrochemical performance of a half cell used in comparative example 1;
figure 9 is a graph of the electrochemical performance of the half cell used in example 6.
Detailed Description
The following is a detailed description of the preferred embodiments of the invention and is not intended to limit the invention in any way, i.e., the invention is not intended to be limited to the embodiments described above, and modifications and alternative compounds that are conventional in the art are intended to be included within the scope of the invention as defined in the claims.
Performance testing
The method for testing the high-voltage cycle performance of the directionally-grown/dissolved lithium anode assembled battery comprises the following steps:
1. assembling the battery: mixing a bismuth compound serving as an active substance with acetylene black and PVDF according to the mass ratio of 8: 1, uniformly dispersing the mixture into slurry by using NMP, coating the slurry on a copper foil with the thickness of 10 microns, drying the copper foil in an oven at the temperature of 80 ℃ for 12 hours, punching the copper foil into a pole piece cathode with the diameter of 13mm, taking a metal lithium piece as a counter electrode, and adopting a 1M LiTFSI/DOL: DME (1: 1 by volume) contains 1% wt LiNO3The electrolyte and the lithium cathode prepared by the invention are assembled into a 2025 button lithium ion battery, and a diaphragm adopts GF/D glass fiber to carry out charge-discharge cycle test. The charge-discharge cycle test was carried out with a compound of metallic bismuth of the same structure as the active material.
Example 1
In commercial Bi2S3The powder is an active substance (the micro morphology of the powder is shown in figure 1), the active substance, acetylene black and PVDF are mixed according to the mass ratio of 8: 1, NMP is used for uniformly dispersing the mixture into slurry, the slurry is coated on a copper foil with the thickness of 10 microns, the copper foil is dried in an oven at the temperature of 80 ℃ for 12 hours, a pole piece with the diameter of 13mm is punched, a lithium metal piece is used as a counter electrode, and a half cell is assembled. Under the same structure, the lithium negative electrode using uncoated copper foil isAnd (4) comparing the samples. Tests show that the lithium metal cathode is 1mA/cm by adopting the lithium ion battery provided by the invention2Charge and discharge current density and 1mAh/cm2The cycle life under the charge-discharge area capacity is more than 2 times of that of a smooth copper foil lithium negative electrode, the average coulombic efficiency is kept above 96.3%, and the stable cycle is more than 140 circles (figure 2).
Example 2
Compared with example 1, the difference is that the bismuth compound used is Bi2O3The method comprises the following specific operations:
with commercial bismuth oxide (Bi)2O3) The powder is used as an active substance (the micro morphology is shown in figure 3), the active substance is mixed with acetylene black and PVDF according to the mass ratio of 8: 1, the mixture is uniformly dispersed into slurry by NMP, the slurry is coated on a copper foil with the thickness of 10 microns, the copper foil is dried in an oven at the temperature of 80 ℃ for 12 hours, a pole piece with the diameter of 13mm is punched, and a metal lithium piece is used as a counter electrode to assemble a half cell. Under the same structure, a lithium negative electrode with uncoated copper foil was used as a comparative sample. Tests have found that the lithium negative electrode with bismuth oxide according to the invention is used at 1mA/cm2Charge and discharge current density and 1mAh/cm2The cycle life under the charge-discharge area capacity is more than 3 times of that of a smooth copper foil lithium negative electrode, the average coulombic efficiency is kept above 96.7%, and the stable cycle is more than 140 circles (figure 4).
Example 3
Compared with example 1, the difference is that the bismuth compound used is BiCl3The method comprises the following specific operations:
with commercial bismuth trichloride (BiCl)3) The powder is used as an active substance (the micro morphology is shown in figure 3), the active substance is mixed with acetylene black and PVDF according to the mass ratio of 8: 1, the mixture is uniformly dispersed into slurry by NMP, the slurry is coated on a copper foil with the thickness of 10 microns, the copper foil is dried in an oven at the temperature of 80 ℃ for 12 hours, a pole piece with the diameter of 13mm is punched, and a metal lithium piece is used as a counter electrode to assemble a half cell. Under the same structure, a lithium negative electrode with uncoated copper foil was used as a comparative sample. Tests have found that the lithium negative electrode with bismuth oxide according to the invention is used at 1mA/cm2Charge and discharge current density and 1mAh/cm2The cycle life under the charge-discharge area capacity is smooth copper foil lithium negativeThe pole is more than 3 times, the average coulombic efficiency is kept more than 97.0%, and the stable cycle is more than 150 circles (figure 5).
Example 4
Compared with example 1, the difference is that the bismuth compound used is BiN3The method comprises the following specific operations:
with commercial bismuth nitride (BiN)3) The powder is used as an active substance, the active substance is mixed with acetylene black and PVDF according to the mass ratio of 8: 1, the mixture is uniformly dispersed into slurry by using NMP, the slurry is coated on a copper foil with the thickness of 10 microns, the copper foil is dried in an oven at the temperature of 80 ℃ for 12 hours, a pole piece with the diameter of 13mm is punched, and a metal lithium piece is used as a counter electrode to assemble a half cell. Assembling a half cell for lithium metal at a current density of 0.1mA/cm2And then, constant-current deposition is carried out for about 10 hours according to the amount of bismuth nitride, and the complete reaction of bismuth nitride and metal lithium is realized, so that the excellent metal lithium cathode material with the lithium bismuth alloy as a substrate and the surface coated with the lithium nitride is prepared. The lithium bismuth alloy is matched with commercial mature lithium cobaltate to assemble a full cell, the capacity retention rate of 200 circles can reach 92.7 percent after stable circulation at 1C, and the lithium bismuth alloy corresponding to the traditional metal bismuth is used as a cathode, so that the effect of obviously improving the capacity retention rate of the lithium bismuth alloy is achieved.
Under the same structure, a lithium negative electrode with uncoated copper foil was used as a comparative sample. Tests have found that the lithium negative electrode with bismuth oxide according to the invention is used at 1mA/cm2Charge and discharge current density and 1mAh/cm2The cycle life at charge-discharge area capacity was more than 3 times that of the smooth copper foil lithium negative electrode (fig. 6).
Example 5
Compared with example 1, the difference is that the bismuth compounds used are bismuth fluoride (BiF) and bismuth nitride (Bi)3N) the composite bismuth material comprises the following specific operations:
using bismuth fluoride (BiF) and bismuth nitride (Bi)3N) ball-milling and uniformly mixing the active substances according to the mass ratio of 1: 1, mixing the active substances with acetylene black and PVDF according to the mass ratio of 8: 1, uniformly dispersing the mixture into slurry by using NMP, coating the slurry on a copper foil with the thickness of 10 microns, drying the slurry in an oven at the temperature of 80 ℃ for 12 hours, punching the slurry into a pole piece with the diameter of 13mm, and assembling a half cell by using a metal lithium piece as a counter electrode. In thatIn the same structure, the lithium negative electrode having an uncoated copper foil was used as a comparative sample. Tests show that the half cell for electrochemically depositing lithium by adopting the two preferable metal bismuth compounds can stably generate an SEI film with the thickness of 30 nanometers, and has good cycle performance at 1mA/cm2Charge and discharge current density and 1mAh/cm2The cycle life under the charge-discharge area capacity is more than 3 times of that of a smooth copper foil lithium negative electrode, the average coulombic efficiency is kept above 97.3%, and the stable cycle is more than 190 circles. (FIG. 7). Coulomb efficiency and cycle number are obviously improved, and performance can be improved by unexpected cooperation in composite use.
Comparative example 1
Elemental metal bismuth is adopted as an active substance, the active substance is mixed with acetylene black and PVDF according to the mass ratio of 8: 1, NMP is used for uniformly dispersing the mixture into slurry, the slurry is coated on copper foil with the thickness of 10 microns, the copper foil is dried in an oven at the temperature of 80 ℃ for 12 hours, a pole piece with the diameter of 13mm is punched, and a metal lithium piece is taken as a counter electrode to assemble a half-cell. Under the same structure, a lithium negative electrode with uncoated copper foil was used as a comparative sample. Tests show that the cycle performance of the half-cell for electrochemically depositing lithium by adopting metal bismuth is improved relative to that of copper foil at 1mA/cm2Charge and discharge current density and 1mAh/cm2The cycle life under the charge-discharge area capacity is more than 1.5 times of that of the smooth copper foil lithium negative electrode, the average coulombic efficiency is kept more than 95%, and the stable cycle is more than 100 circles (figure 8). However, the lithium bismuth alloy negative electrode produced by using the compound without bismuth as an active material has excellent performance.
Example 6
Compared with the embodiment 1, the difference is that the performance of the lithium bismuth alloy cathode produced by wetting with molten lithium is as follows:
mixing bismuth oxide (Bi2O3) as an active substance with acetylene black and PVDF according to the mass ratio of 8: 1, uniformly dispersing the mixture into slurry by using NMP, coating the slurry on a copper foil with the thickness of 10 microns, drying the copper foil in an oven at the temperature of 80 ℃ for 12 hours, and punching the slurry into a pole piece with the diameter of 13mm, wherein the mass of the active substance bismuth oxide is 2mg/cm 210 microns thick; and (5) assembling the half cell by taking the metal lithium sheet as a counter electrode. Under the same structure, by meltingThe lithium soaking method converts all bismuth oxide on the pole piece into metal lithium bismuth alloy (the lithium content is about 3 mAh). At 1mA/cm2Charge and discharge current density and 1mAh/cm2Cycling at charge-discharge area capacity. Tests show that the negative polarity of the lithium bismuth alloy prepared by soaking molten lithium is slightly improved, but the negative electrode prepared without the electrochemical deposition of the metal lithium has long service life which is only close to 100 cycles, and the coulombic efficiency is not as high as the negative electrode prepared with the electrochemical deposition of the metal lithium and is only 94%. (FIG. 9).
Claims (5)
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| CN111370698A (en) * | 2020-03-09 | 2020-07-03 | 北京纳米能源与系统研究所 | Composite metal material, preparation method and application thereof, high-energy-density battery and symmetrical button battery |
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| CN118867131A (en) * | 2023-04-12 | 2024-10-29 | 杭州建德盛开新材料有限公司 | Negative electrode sheet for lithium secondary battery, preparation method thereof, lithium secondary battery and electric device |
| CN120072857A (en) * | 2023-11-22 | 2025-05-30 | 广州汽车集团股份有限公司 | Negative pole piece and preparation method and application thereof |
| CN120878753A (en) * | 2024-04-22 | 2025-10-31 | 广州汽车集团股份有限公司 | Negative electrode without current collector, preparation method of negative electrode, battery and power utilization device |
| CN118867142B (en) * | 2024-07-04 | 2026-04-28 | 合肥工业大学 | A method for preparing a bismuth/fluorine/nitrogen hybrid protective layer for lithium metal anodes and its application |
| CN119230704A (en) * | 2024-09-05 | 2024-12-31 | 湘潭大学 | A method for preparing a negative electrode current collector for a sodium metal battery and its application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1591936A (en) * | 2003-09-05 | 2005-03-09 | 日本电池株式会社 | Lithium contained substrate and method for mfg non-aqueous electrolyte electrochemical accomulation apparatus containing the same |
| CN1729586A (en) * | 2002-05-24 | 2006-02-01 | 日本电气株式会社 | The negative pole that rechargeable battery is used and use its rechargeable battery |
| CN1754275A (en) * | 2002-12-23 | 2006-03-29 | A123系统公司 | High energy and high power density electrochemical cells |
| KR20090078128A (en) * | 2008-01-14 | 2009-07-17 | 한양대학교 산학협력단 | Cathode active material for lithium secondary battery, preparation method thereof, and lithium secondary battery comprising same |
| TW201330352A (en) * | 2012-01-06 | 2013-07-16 | Univ Nat Taiwan Science Tech | Anode protector of lithium-ion battery and method for fabricating the same |
-
2018
- 2018-07-31 CN CN201810859419.0A patent/CN110783529B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1729586A (en) * | 2002-05-24 | 2006-02-01 | 日本电气株式会社 | The negative pole that rechargeable battery is used and use its rechargeable battery |
| CN1754275A (en) * | 2002-12-23 | 2006-03-29 | A123系统公司 | High energy and high power density electrochemical cells |
| CN1591936A (en) * | 2003-09-05 | 2005-03-09 | 日本电池株式会社 | Lithium contained substrate and method for mfg non-aqueous electrolyte electrochemical accomulation apparatus containing the same |
| KR20090078128A (en) * | 2008-01-14 | 2009-07-17 | 한양대학교 산학협력단 | Cathode active material for lithium secondary battery, preparation method thereof, and lithium secondary battery comprising same |
| TW201330352A (en) * | 2012-01-06 | 2013-07-16 | Univ Nat Taiwan Science Tech | Anode protector of lithium-ion battery and method for fabricating the same |
Non-Patent Citations (1)
| Title |
|---|
| 铋基复合碳纳米纤维储锂性能与In2O3纳米棒气敏性能的研究;唐云晶;《中国优秀硕士学位论文全文数据库（电子期刊）》;20160520;第21-23、31-34页 * |
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