CN119349647B - Lithium ferrite lithium supplementing agent prepared by stepwise lithium adding method and preparation method thereof - Google Patents
Lithium ferrite lithium supplementing agent prepared by stepwise lithium adding method and preparation method thereof Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 135
- JXGGISJJMPYXGJ-UHFFFAOYSA-N lithium;oxido(oxo)iron Chemical compound [Li+].[O-][Fe]=O JXGGISJJMPYXGJ-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 230000001502 supplementing effect Effects 0.000 title description 41
- 238000005245 sintering Methods 0.000 claims abstract description 77
- 239000002243 precursor Substances 0.000 claims abstract description 70
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000654 additive Substances 0.000 claims abstract description 18
- 239000000047 product Substances 0.000 claims abstract description 16
- 239000013589 supplement Substances 0.000 claims abstract description 15
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 43
- 229910052799 carbon Inorganic materials 0.000 claims description 42
- 238000002156 mixing Methods 0.000 claims description 24
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 230000000996 additive effect Effects 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 4
- 229960004887 ferric hydroxide Drugs 0.000 claims description 3
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 3
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 claims description 3
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- 238000007580 dry-mixing Methods 0.000 claims description 2
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 2
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 2
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 239000007791 liquid phase Substances 0.000 abstract description 4
- 150000002506 iron compounds Chemical class 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 description 59
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000012360 testing method Methods 0.000 description 17
- 238000001816 cooling Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000007873 sieving Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000006138 lithiation reaction Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
- C01G49/0027—Mixed oxides or hydroxides containing one alkali metal
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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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
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
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- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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Abstract
本发明公开了一种分步加锂法制备的铁酸锂补锂剂及其制备方法，首先将全部铁源和部分锂源以及添加剂混合烧结制备出前驱体，再将前驱体和剩下的锂源混合制备成品，减少第二步烧结所用的锂源量，减少高温状态下锂液相熔融体的量，使所有元素均匀分布，材料性能优异，且在制备前驱体时可以使用空气气氛烧结，也可以使用碳酸锂为锂源并不带入额外杂质；其中空气气氛烧结可以降低成本，并且铁源不受限制，可以用低价态的铁化合物；碳酸锂做为锂源在工艺上和成本上都有很大益处。
The invention discloses a lithium ferrite lithium supplement prepared by a step-by-step lithium addition method and a preparation method thereof. Firstly, all iron sources, part of lithium sources and additives are mixed and sintered to prepare a precursor, and then the precursor and the remaining lithium source are mixed to prepare a finished product, thereby reducing the amount of lithium source used in the second step of sintering and reducing the amount of lithium liquid phase melt under a high temperature state, so that all elements are evenly distributed, and the material has excellent performance. When preparing the precursor, air atmosphere sintering can be used, and lithium carbonate can also be used as a lithium source without introducing additional impurities; wherein air atmosphere sintering can reduce costs, and the iron source is not limited, and low-valent iron compounds can be used; lithium carbonate as a lithium source has great advantages in terms of process and cost.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium ferrite lithium supplementing agent prepared by a stepwise lithium adding method and a preparation method thereof.
Background
The lithium ion battery has the advantages of higher energy density, better cycle performance, higher working voltage, no memory effect and the like, is widely applied to various fields of 3C digital, power and energy storage, and is one of the most promising energy sources at present.
However, in the first charge and discharge process of the lithium ion battery, an SEI film is generated on the surface of the negative electrode, and a large amount of lithium ions are consumed in the process, which means that the lithium ion part separated from the positive electrode material is irreversibly consumed, so that the first coulomb efficiency and reversible capacity of the battery are reduced. In a graphite negative electrode lithium battery, the first charge consumes about 10% of the lithium source. In a re-alloyed or silicon negative lithium battery, lithium consumption is higher than 10%.
To solve this problem, there are currently mainly methods of pre-lithiation of the negative electrode material, pre-lithiation of the positive electrode material, and pre-lithiation of the electrode sheet. The preparation method has the advantages of simple process and low cost of the positive electrode material pre-lithiation, and is a preferred method for industrialization. The pre-lithiation of the positive electrode material is mainly to add a lithium supplementing agent into the positive electrode material, the capacity of the lithium ferrite series material is more than 800mAh/g, the working voltage window is consistent with that of a conventional lithium ion battery, and the positive electrode material does not participate in the electrochemical process basically in the later stage, so that the lithium supplementing agent has a wide prospect.
However, the chemical formula of lithium ferrite contains a great amount of lithium, and the conventional preparation method is to add all lithium sources in one step and then mix and sinter the lithium sources, so that the quality of ① lithium sources is usually much higher than that of iron sources, and the lithium sources are easy to mix unevenly, so that local lithium overdose is caused. ② The large lithium content causes the mixture to form a large amount of lithium liquid phase melt when sintered in a kiln, and causes uneven distribution of materials (iron sources or additives) with large specific gravity differences.
Disclosure of Invention
Aiming at the problems that the chemical formula of lithium ferrite contains a great amount of lithium, the conventional preparation method is to add all lithium sources in one step and then mix and sinter the lithium sources, so that the mixing is uneven, the local lithium is excessive, and a great amount of lithium liquid phase melt is formed when the mixture is sintered in a kiln due to the huge lithium content, so that the material (iron source or additive) with great specific gravity difference is unevenly distributed.
The invention aims to provide a stepwise lithium adding preparation method of lithium ferrite, which comprises the steps of preparing a precursor containing lithium and preparing the lithium ferrite by using the precursor. Aims to solve the problem caused by the need of using a large amount of lithium sources in the preparation process.
The technical scheme of the invention is as follows:
the preparation method comprises the following steps:
the preparation of the precursor comprises the steps of mixing an iron source, a lithium source and an additive, and sintering the mixture to obtain the precursor, wherein the molar ratio of the lithium source to the additive is: mixing, wherein M is an added metal element;
precursor coating, namely mixing the precursor with a coating substance and sintering to obtain a coated precursor;
the preparation of the finished product, namely, mixing the coated precursor with a lithium source and sintering to obtain a lithium ferrite lithium supplementing agent;
Li xFeyM(1-y)Oz, wherein M is an additive metal element, x is more than or equal to 4.9 and less than or equal to 5.3,0.8, y is more than or equal to 1, and z=0.5× (x+3).
The aim of the invention is achieved by the following technical scheme:
The preparation method of the lithium ferrite lithium supplementing agent by the stepwise lithium adding method comprises the following steps:
S1, preparing a precursor, namely preparing a lithium source, an iron source and an additive according to the molar ratio Mixing, wherein M is an added metal element, and sintering and crushing the mixture to obtain a precursor;
The lithium source is selected from one of lithium carbonate, lithium nitrate, lithium hydroxide monohydrate, anhydrous lithium hydroxide, lithium oxalate and lithium oxide;
The iron source is selected from one of ferrous oxide, ferric hydroxide, ferrous hydroxide, ferric oxalate and ferric nitrate;
the additive is various metal element compounds which are required to be doped, wherein the doping metal elements are Co, W, ca, al, mg, zn, sb, rare earth elements and the like;
S2, coating a precursor, namely mixing the precursor obtained in the previous step with a carbon source, and sintering to obtain a carbon-coated precursor, wherein the mass ratio of the precursor to the carbon in the carbon source is as follows The carbon source is selected from glucose, sucrose and the like;
S3, preparing a finished product, namely mixing the coated precursor obtained in the previous step with a lithium source, sintering, crushing and sieving the sintered product to obtain a lithium ferrite lithium supplementing agent, wherein the chemical formula of the lithium ferrite is Li xFeyM(1-y)Oz, M is an additive metal element, x is more than or equal to 4.9 and less than or equal to 5.3,0.8 and less than or equal to y is less than or equal to 1, and z=0.5× (x+3);
the lithium source and the precursor are mixed according to the molar ratio Mixing;
the sintering described in S3, wherein the sintering temperature is Sintering time isThe sintering atmosphere is a mixed gas of a reducing atmosphere and an inert gas;
The obtained lithium ferrite lithium supplementing agent has the following performance indexes that the first charge capacity is more than 690mAh/g and the first discharge capacity is less than 14mAh/g.
Further, the mixing in the steps S1, S2 and S3 is dry mixing, and may be performed by a ball mill mixer, a high-speed mixer or the like.
Further, sintering the mixture in the step S1 to obtain a precursor, wherein the sintering temperature is as followsSintering time isThe sintering atmosphere is air, and the sintering temperature in the step S2 isSintering time isThe sintering atmosphere is an inert atmosphere, and may be an inert gas such as nitrogen or argon, and nitrogen is preferable in view of cost.
Further, the additives described in step S1 are selected such that the compounds are selected to have no additional impurities, and such that the particle size and the particle size of the starting material are close to or smaller.
Further, the mass ratio of the precursor and carbon in the carbon source in step S2 is preferably 100:10.
Further, the sintering in step S3 is performed in a reducing atmosphere, and in order to ensure that carbon of the precursor lithium is not oxidized, a reducing atmosphere including hydrogen and hydrocarbon gas is used, and in order to ensure safety and reduce cost, a mixture of a reducing gas and an inert gas is used.
The invention also relates to a lithium ferrite lithium supplementing agent prepared by the step-by-step lithium adding method, which is prepared by the preparation method of the lithium ferrite lithium supplementing agent prepared by the step-by-step lithium adding method, wherein the chemical formula of the lithium ferrite is Li xFeyM(1-y)Oz, M is an additive metal element, x is more than or equal to 4.9 and less than or equal to 5.3,0.8 and less than or equal to 1, z=0.5× (x+3), the lithium ferrite lithium supplementing agent has the advantages of high crystallinity, high purity, no impurity phase, high initial charge capacity and small discharge capacity, and has the following performance indexes of initial charge capacity of more than 690 mAh/g and initial discharge capacity of less than 14 mAh/g.
Compared with the prior art, the invention has the following advantages:
1. According to the preparation method of the lithium ferrite lithium supplementing agent prepared by the stepwise lithium adding method, all iron sources, part of lithium sources and additives are mixed and sintered to prepare a precursor, the precursor and the rest of lithium sources are mixed to prepare a finished product, the amount of the lithium sources used in the second step of sintering is reduced, the amount of lithium liquid phase melt in a high-temperature state is reduced, all elements are uniformly distributed, the material performance is excellent, air atmosphere sintering can be used for preparing the precursor, lithium carbonate can be used as the lithium sources and does not bring additional impurities, the air atmosphere sintering can reduce cost, the iron sources are not limited, low-valence iron compounds can be used, and the lithium carbonate has great benefits in process and cost as the lithium sources.
2. According to the lithium ferrite lithium supplementing agent prepared by the stepwise lithium adding method, the doping elements are added into the precursor, the doping elements can be selected to be increased in variety due to the fact that the precursor is sintered in the air atmosphere, low-cost compounds can be selected, the amount of lithium sources used by the precursor is not large, and the situation that the additives are unevenly distributed due to the fact that the difference between the amount of main raw materials and the amount of additives is large is avoided.
3. According to the lithium ferrite lithium supplementing agent prepared by the stepwise lithium adding method, the precursor is subjected to carbon coating, and the carbon-coated precursor and a lithium source are mixed and sintered, so that carbon can be uniformly distributed in the lithium ferrite, and the conductivity of the lithium ferrite is improved.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention.
FIG. 1 is an SEM image of a precursor in a preparation method of a lithium ferrite lithium-supplementing agent by a stepwise lithium-adding method according to example 1 of the present invention;
FIG. 2 is an XRD pattern of a finished product obtained by a preparation method of a lithium ferrite lithium supplementing agent prepared by a stepwise lithium adding method in embodiment 1 of the invention;
FIG. 3 is an XRD pattern of a finished product obtained by a preparation method of a lithium ferrite lithium supplement agent prepared by a stepwise lithium addition method in example 2 of the present invention;
FIG. 4 is an XRD pattern of a finished product obtained by a preparation method of a lithium ferrite lithium supplement agent prepared by a stepwise lithium addition method in example 3 of the present invention;
FIG. 5 is an XRD pattern of a finished product obtained by a preparation method of a lithium ferrite lithium supplement agent prepared by a stepwise lithium addition method in example 4 of the present invention;
fig. 6 is an XRD pattern of the finished product prepared in comparative example 1.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
The preparation method of the lithium ferrite lithium supplementing agent by the stepwise lithium adding method comprises the following steps:
S1, preparing a precursor, namely weighing 93.72g of lithium carbonate, 167.51g of ferric oxide and 4.88g of tungsten oxide according to a molar ratio of Li (Fe+W) =1.2:1 (wherein Fe is 0.99 and W is 0.01), uniformly mixing and sintering,
Wherein the sintering temperature is 800 ℃, the sintering time is 1h, the sintering atmosphere is air, the mixture is cooled to room temperature and taken out, and then the mixture is crushed to obtain a precursor;
S2, coating a precursor, namely uniformly mixing the precursor obtained in the previous step with a carbon source, and sintering, wherein the sintering temperature is 200 ℃, the sintering time is 3 hours, the sintering atmosphere is nitrogen, cooling to room temperature and taking out to obtain the precursor coated with carbon, wherein the mass ratio of carbon in the precursor and the carbon source is 200g to 50g, and the carbon source is selected from glucose;
S3, preparing a finished product, namely mixing 203.41g of the carbon-coated precursor obtained in the previous step with 577.01g of lithium nitrate according to a molar ratio of Li to Fe=3.9:1, sintering, wherein the sintering temperature is 700 ℃, the sintering time is 10 hours, the sintering atmosphere is a reducing atmosphere (3% hydrogen and 97% nitrogen), cooling to room temperature, taking out, crushing and sieving to obtain the lithium ferrite lithium supplementing agent.
The obtained lithium ferrite lithium supplementing agent has the following performance indexes:
the first charge capacity is 697mAh/g, the discharge capacity is 9mAh/g, and the buckling test method is shown in the following test example for testing the lithium supplementing agent capacity.
FIG. 1 is an SEM image of the precursor in step S1, the precursor being single crystal particles of uniform size;
fig. 2 is an XRD pattern of the lithium ferrite lithium-supplementing agent, and it can be seen from the figure that the prepared lithium ferrite lithium-supplementing agent is consistent with diffraction peaks of PDF cards.
Example 2:
The preparation method of the lithium ferrite lithium supplementing agent by the stepwise lithium adding method comprises the following steps:
s1, preparing a precursor, namely weighing 89.81g of lithium carbonate, 155.78g of ferroferric oxide and 2.95g of calcium oxide according to a molar ratio of Li (Fe+Ca) =1.15:1 (wherein Fe is 0.95 and Ca is 0.05), uniformly mixing and sintering, wherein the sintering temperature is 700 ℃, the sintering time is 2 hours, the sintering atmosphere is air, cooling to room temperature, taking out, and crushing the materials to obtain the precursor;
S2, coating a precursor, namely uniformly mixing the precursor obtained in the previous step with a carbon source, and sintering, wherein the sintering temperature is 300 ℃, the sintering time is 2 hours, the sintering atmosphere is nitrogen, cooling to room temperature and taking out to obtain the precursor coated with carbon, wherein the mass ratio of carbon in the precursor and the carbon source is 200g to 50g, and the carbon source is selected from glucose;
S3, preparing a finished product, namely mixing 203.41g of the carbon-coated precursor obtained in the previous step with 128.25g of lithium oxide according to a molar ratio of Li to Fe=4.0:1, sintering, wherein the sintering temperature is 800 ℃, the sintering time is 4 hours, the sintering atmosphere is a reducing atmosphere (3% hydrogen+97% nitrogen), cooling to room temperature, taking out, crushing and sieving to obtain a lithium ferrite lithium supplementing agent;
The obtained lithium ferrite lithium supplementing agent has the following performance indexes:
the first charge capacity is 694mAh/g, the discharge capacity is 10mAh/g, and the buckling test method is shown in the following test example for testing the lithium supplementing agent capacity.
Fig. 3 is an XRD pattern of the lithium ferrite lithium-supplementing agent, and it can be seen from the figure that the prepared lithium ferrite lithium-supplementing agent is consistent with diffraction peaks of PDF cards.
Example 3:
The preparation method of the lithium ferrite lithium supplementing agent by the stepwise lithium adding method comprises the following steps:
S1, preparing a precursor, namely weighing 97.94g of lithium hydroxide and 226.58g of ferric hydroxide according to a molar ratio of Li to Fe=1.1:1, uniformly mixing, sintering at a sintering temperature of 600 ℃ for 3 hours in a sintering atmosphere of air, cooling to room temperature, taking out, and crushing the materials to obtain the precursor;
s2, coating a precursor, namely uniformly mixing the precursor obtained in the previous step with a carbon source, and sintering, wherein the sintering temperature is 400 ℃, the sintering time is 1h, the sintering atmosphere is nitrogen, cooling to room temperature and taking out to obtain the precursor coated with carbon, wherein the mass ratio of carbon in the precursor and the carbon source is 200g to 50g, and the carbon source is selected from glucose;
S3, preparing a finished product, namely mixing 203.41g of the carbon-coated precursor obtained in the previous step with 369.03g of lithium hydroxide according to a molar ratio of Li to Fe=4.1:1, sintering, wherein the sintering temperature is 800 ℃, the sintering time is 6 hours, the sintering atmosphere is a reducing atmosphere (5% hydrogen+95% nitrogen), cooling to room temperature, taking out, crushing and sieving to obtain a lithium ferrite lithium supplementing agent;
The obtained lithium ferrite lithium supplementing agent has the following performance indexes:
the first charge capacity is 709mAh/g, the discharge capacity is 13.4mAh/g, and the buckling test method is detailed in the following test example lithium supplementing agent capacity test step.
Fig. 4 is an XRD pattern of the lithium ferrite lithium-supplementing agent, and it can be seen from the figure that the prepared lithium ferrite lithium-supplementing agent is consistent with diffraction peaks of PDF cards.
Example 4:
The preparation method of the lithium ferrite lithium supplementing agent by the stepwise lithium adding method comprises the following steps:
S1, preparing a precursor, namely weighing 145.75g of lithium nitrate, 186.59g of ferrous hydroxide and 3.15g of cobalt oxide according to a molar ratio of Li (Fe+Co) =1:1 (wherein Fe is 0.98 and Co is 0.02), uniformly mixing and sintering, wherein the sintering temperature is 500 ℃, the sintering time is 4 hours, the sintering atmosphere is air, cooling to room temperature, taking out, and crushing the materials to obtain the precursor;
s2, coating a precursor, namely uniformly mixing the precursor obtained in the previous step with a carbon source, and sintering, wherein the sintering temperature is 400 ℃, the sintering time is 1h, the sintering atmosphere is nitrogen, cooling to room temperature and taking out to obtain the precursor coated with carbon, wherein the mass ratio of carbon in the precursor and the carbon source is 200g to 50g, and the carbon source is selected from glucose;
S3, preparing a finished product, namely mixing 203.41g of the carbon-coated precursor obtained in the previous step with 378.03g of lithium hydroxide according to a molar ratio of Li to Fe=4.2:1, sintering at a sintering temperature of 900 ℃ for 6 hours, cooling to room temperature in a reducing atmosphere (5% hydrogen+95% nitrogen), taking out, crushing and sieving to obtain a lithium ferrite lithium supplementing agent;
The obtained lithium ferrite lithium supplementing agent has the following performance indexes:
The first charge capacity is 746mAh/g, the discharge capacity is 12mAh/g, and the buckling test method is shown in the following test example lithium supplementing agent capacity test step.
Fig. 5 is an XRD pattern of the lithium ferrite lithium-supplementing agent, and it can be seen from the figure that the prepared lithium ferrite lithium-supplementing agent is consistent with diffraction peaks of PDF cards.
Comparative example 1:
comparative example 1 differs from example 1 in that comparative example 1 uses a one-shot lithium addition method and example 1 uses a stepwise lithium addition method.
Weighing 472.54g of lithium hydroxide and 171.76g of ferric oxide according to a molar ratio of Li to Fe=5.2:1, heating to 900 ℃ in mixed reducing gas (5% hydrogen and 95% nitrogen), preserving heat for 6 hours, cooling to room temperature, taking out, crushing and sieving to obtain a lithium ferrite lithium supplementing agent;
The obtained lithium ferrite lithium supplementing agent has the following performance indexes:
The first charge capacity is 201mAh/g, the discharge capacity is 12.1mAh/g, and the buckling test method is detailed in the following test example lithium supplementing agent capacity test step.
FIG. 6 shows XRD patterns of the lithium ferrite lithium-supplementing agent, and it can be seen from the patterns that the lithium ferrite lithium-supplementing agent has a hetero-phase peak and has low purity.
Comparative example 2:
Comparative example 1 differs from example 2 in that comparative example 2 uses a one-shot lithium addition method and example 2 uses a stepwise lithium addition method.
Weighing 170.03g of lithium oxide and 182.17g of ferric oxide according to a molar ratio of Li to Fe=5.0:1, heating to 800 ℃ in mixed reducing gas (3% hydrogen and 97% nitrogen), preserving heat for 4 hours, cooling to room temperature, taking out, crushing and sieving to obtain a lithium ferrite lithium supplementing agent;
The obtained lithium ferrite lithium supplementing agent has the following performance indexes:
the first charge capacity is 97mAh/g, the discharge capacity is 12.6mAh/g, and the buckling test method is detailed in the following test example lithium supplementing agent capacity test step.
Experimental example:
and (3) testing the capacity of the lithium supplementing agent:
the lithium supplement agents prepared in the examples and the comparative examples are prepared into button half-cell test capacities, and the specific steps are as follows:
weighing a lithium supplementing agent, namely carbon black, namely PVDF=25:8:1:1 according to the mass ratio, uniformly mixing, coating on an aluminum foil, drying in a vacuum oven, cutting into round pieces, and assembling a metal lithium cathode, a diaphragm and an electrolyte into a CR2032 button half-cell;
Battery test conditions, 0.1C charge and discharge, voltage 。
Results and discussion:
The following are the capacity test results of the examples and comparative examples:
TABLE 1 results of examples and comparative examples Capacity tests
1. As can be seen from the comparison of examples 1-4 and comparative example 1, the capacity results show that the preparation method of the lithium ferrite lithium supplement agent prepared by the stepwise lithium adding method provided by the invention has the advantages that the prepared lithium ferrite lithium supplement agent has no impurity phase peak, the purity is very high, the corresponding capacity is very high, the first charge capacity is more than 690mAh/g and is 694-746mAh/g, the first charge capacity can reach 746mAh/g at the highest, and the first discharge capacity is less than 14mAh/g and is 9.0-13.4mAh/g. The lithium ferrite lithium supplementing agent prepared in the comparative example 1 adopts a one-time lithium adding method, has a lot of impurity phases, low sample purity and low corresponding capacity, and is 97-201mAh/g, and the minimum capacity is only 97mAh/g.
2. In addition, 4 embodiments of the invention adopt different lithium sources and iron sources, the prepared lithium ferrite lithium-supplementing agent can reach higher first charge capacity, and the total charge capacity is larger than 690mAh/g, so that the preparation method of the lithium ferrite lithium-supplementing agent prepared by the stepwise lithium adding method is high in process flexibility, can be suitable for different production lines and is convenient for industrialization.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (4)
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| CN118431477A (en) * | 2024-06-05 | 2024-08-02 | 陕西煤业化工技术研究院有限责任公司 | A positive electrode lithium supplement and preparation method thereof |
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