CN112678793A - High-capacity high-pressure-density lithium battery positive electrode material and preparation method thereof - Google Patents
High-capacity high-pressure-density lithium battery positive electrode material and preparation method thereof Download PDFInfo
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- CN112678793A CN112678793A CN202011474572.5A CN202011474572A CN112678793A CN 112678793 A CN112678793 A CN 112678793A CN 202011474572 A CN202011474572 A CN 202011474572A CN 112678793 A CN112678793 A CN 112678793A
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- lithium
- lithium salt
- positive electrode
- electrode material
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 29
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000005245 sintering Methods 0.000 claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000010416 ion conductor Substances 0.000 claims abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000006258 conductive agent Substances 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- 239000010405 anode material Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 12
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 10
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000005955 Ferric phosphate Substances 0.000 claims description 6
- 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
- 229940032958 ferric phosphate Drugs 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- 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 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
- 235000007144 ferric diphosphate Nutrition 0.000 claims description 4
- 239000011706 ferric diphosphate Substances 0.000 claims description 4
- CADNYOZXMIKYPR-UHFFFAOYSA-B ferric pyrophosphate Chemical compound [Fe+3].[Fe+3].[Fe+3].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O CADNYOZXMIKYPR-UHFFFAOYSA-B 0.000 claims description 4
- 229940036404 ferric pyrophosphate Drugs 0.000 claims description 4
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 4
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 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
- 239000008117 stearic acid Substances 0.000 claims description 4
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 3
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 claims description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 239000005639 Lauric acid Substances 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- JHFZWTMEVGPUTE-UHFFFAOYSA-L dilithium;2-hydroxybutanedioate Chemical compound [Li+].[Li+].[O-]C(=O)C(O)CC([O-])=O JHFZWTMEVGPUTE-UHFFFAOYSA-L 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
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- ATEAWHILRRXHPW-UHFFFAOYSA-J iron(2+);phosphonato phosphate Chemical compound [Fe+2].[Fe+2].[O-]P([O-])(=O)OP([O-])([O-])=O ATEAWHILRRXHPW-UHFFFAOYSA-J 0.000 claims description 2
- 229940071264 lithium citrate Drugs 0.000 claims description 2
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 claims description 2
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 2
- AZEPWULHRMVZQR-UHFFFAOYSA-M lithium;dodecanoate Chemical compound [Li+].CCCCCCCCCCCC([O-])=O AZEPWULHRMVZQR-UHFFFAOYSA-M 0.000 claims description 2
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 229960004838 phosphoric acid Drugs 0.000 claims description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 239000005696 Diammonium phosphate Substances 0.000 claims 1
- 239000006012 monoammonium phosphate Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 238000005056 compaction Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 4
- 238000006722 reduction reaction Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 15
- 238000012360 testing method Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229910052493 LiFePO4 Inorganic materials 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 238000001354 calcination Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000000498 ball milling Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 6
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 229910015818 MPO4 Inorganic materials 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229960004793 sucrose Drugs 0.000 description 3
- 229910010951 LiH2 Inorganic materials 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910017677 NH4H2 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000010450 olivine Substances 0.000 description 2
- 229910052609 olivine Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910016051 LixMPO4 Inorganic materials 0.000 description 1
- WFGBXPXOFAFPTO-UHFFFAOYSA-N [P].[Fe].[Li] Chemical compound [P].[Fe].[Li] WFGBXPXOFAFPTO-UHFFFAOYSA-N 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229960001031 glucose Drugs 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
Classifications
-
- 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
Abstract
The invention discloses a high-capacity high-pressure-density lithium battery positive electrode material and a preparation method thereof. The method comprises the following steps: 1) adding a part of lithium salt into a solvent, and grinding or crushing the lithium salt to a certain particle size; 2) mixing another part of lithium salt, a phosphorus source, an iron source and a conductive agent with the lithium salt in the step 1), adding a certain amount of solvent for grinding, and drying to obtain a precursor; 3) sintering the precursor obtained in the step 2) under the protection of inert atmosphere to obtain the lithium battery anode material. According to the method, a part of lithium salt is ground to a certain particle size, under the high-temperature sintering condition, the reaction activity of small lithium salt particles is high, the carbothermic reduction reaction can be preferentially carried out, and meanwhile, a fast ion conductor compound can be generated, so that the electronic conductivity of the material is improved, the impedance is reduced, and the positive electrode material with good size gradation and particle dispersibility can be obtained, so that the compaction density of the positive electrode material is improved, and meanwhile, the high capacity can be kept. The preparation process is simple and easy to realize industrial production.
Description
Technical Field
The invention relates to the field of lithium batteries, in particular to a high-capacity high-pressure-density lithium battery positive electrode material and a preparation method thereof.
Background
The lithium ion battery as a new generation of green high-energy battery has the advantages of high energy density, good cycle performance, small self-discharge and no phenomenonMemory effect, wide working temperature range, etc. Cathode material Li of olivine structurexMPO4As a new generation of lithium ion battery cathode material, the lithium ion battery cathode material has the advantages of stable structure, good safety, good thermal stability, super long cycle life and rich raw material sources, is the most potential lithium ion battery cathode material at present, and is suitable for large-scale application in the aspects of electric vehicles, energy storage batteries and the like.
The cathode material of olivine structure, which is currently widely studied, has low electronic and ionic conductivities due to the structural characteristics of its compounds. Improving conductivity by coating a easily conductive substance, or synthesizing a product having nano-sized particles to shorten a lithium ion diffusion path is a major method for solving low electronic conductivity and low ionic conductivity. But carbon-coated or nanosized LixMPO4The low compaction density leads to low volumetric specific capacity, which increases the cost of the battery on the one hand and limits the range of applications of the material on the other hand.
Currently, the cathode material Li is improvedxMPO4The main method for compacting the density is 1. by increasing the sintering temperature or extending the sintering time, there is a disadvantage in that the particle size increases or miscellaneous items are generated after increasing the sintering temperature, thereby causing a capacity decrease. 2. By using the precursor with larger primary particles, the defects are that the grinding is difficult in the material mixing process, the energy consumption is increased, and the difficulty in preparing the precursor is high. 3. By multiple compaction or sintering, Li with higher compaction density is obtainedxMPO4The disadvantages of complex process, high energy consumption and poor operability.
Disclosure of Invention
The invention provides a preparation method of a high-capacity high-pressure-density lithium battery positive electrode material, which is characterized in that a part of lithium salt is crushed or ground to a certain particle size, then other materials are added into slurry for continuous grinding, and the lithium battery positive electrode material is obtained through drying and sintering. The lithium salts with different particle sizes and the compounds of transition metals have different reaction activities in the sintering process, so that the anode materials with different particle sizes can be obtained, the lithium salts with small particles react with the compounds of transition metals more fully, and the anode is obtainedThe material particles are better dispersed, so that the capacity of the sample can be maintained while the compaction density is improved. The method comprises grinding lithium salt to obtain Li with large and small particle sizexMPO4The method is beneficial to improving the compacted density and simultaneously can keep higher discharge capacity.
The technical scheme adopted by the invention is as follows:
a preparation method of a high-capacity high-pressure-density lithium battery positive electrode material comprises the following steps:
1) adding a part of lithium salt into a solvent, and grinding or crushing the lithium salt to a certain particle size;
2) mixing another part of lithium salt, phosphorus source, iron source and conductive agent with the lithium salt in the step 1), adding a certain amount of solvent for grinding, and drying to obtain a precursor
3) Sintering the precursor obtained in the step 2) under the protection of inert atmosphere to obtain the lithium battery anode material containing the fast ion conductor compound.
Further, grinding or crushing the lithium salt to 50-10000 nm in the step 1); and 2) grinding in a ball mill to 50-800 nm.
Further, the lithium salt in the step 1) accounts for 5-95% of the total amount of the lithium salt.
Further, the lithium salt in step 1) and step 2) includes: one or more of lithium carbonate, lithium dihydrogen phosphate, lithium hydroxide, lithium oxalate, lithium formate, lithium silicate, lithium laurate, lithium malate and lithium citrate.
Further, the phosphorus source in the step 2) is one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, lithium dihydrogen phosphate, phosphoric acid, ferric phosphate, pyrophosphoric acid, ferric pyrophosphate and ferric phosphate dihydrate.
Further, the iron source in the step 2) is one or more of iron phosphate, ferrous pyrophosphate, ferric pyrophosphate, ferrous oxide, ferric oxide, basic ferric oxide, ferroferric oxide and ferric phosphate dihydrate.
Further, the conductive agent in step 2) includes: one or more of acetylene black, graphite, citric acid, ascorbic acid, sucrose, glucose, cellulose, phenolic resin, CNT, adipic acid, PEG, stearic acid, lauric acid.
Further, the solvent in step 1) comprises water, an organic solvent or a mixed solution of the water and the organic solvent.
Further, the fast ion conductor compound in step 3) is an iron-phosphorus-lithium compound, such as Fe2P、FeP、Fe3P、Li3PO4、Li4P2O7One or more of.
Further, the sintering is carried out at 730-800 ℃ in the step 3), and the sintering time is preferably 20-40 h.
The invention also provides a high-capacity high-pressure-density lithium battery positive electrode material prepared by adopting the method.
According to the invention, the lithium salt is ground and crushed firstly, the particle size of the lithium salt is controlled, and during the sintering reaction process, the small-particle lithium salt has high reaction activity, can preferentially perform a carbothermic reduction reaction, and can generate a fast ion conductor compound, so that the electronic conductivity of the material is improved, the impedance is reduced, the generation of the positive electrode material with good monodispersity and particle size gradation is facilitated, and the compaction density and the capacity of the product are improved. The invention has the beneficial effects that: 1. the operation is simple, and the process is simple; 2. the obtained product has high compaction density and high capacity.
Drawings
Fig. 1 is a scanning electron micrograph of high-capacity high-compaction lithium iron phosphate prepared in example 1 of the present invention.
Fig. 2 is a capacity test graph of the high-capacity high-pressure-dense lithium iron phosphate prepared in example 1 of the present invention.
Fig. 3 is an EDS spot scan of the high capacity, high compaction lithium iron phosphate prepared in example 1 of the present invention.
Fig. 4 is an EIS test chart of the high-capacity high-pressure-dense lithium iron phosphate prepared in example 1 of the present invention. Wherein the abscissa represents the electrochemical impedance of the real part in Z'/Ohm, and the ordinate represents the electrochemical impedance of the imaginary part in-Z "/Ohm.
Fig. 5 is a scanning electron micrograph of the high-capacity, high-compaction lithium iron phosphate prepared in comparative example 1.
Fig. 6 is a capacity test graph of the high-capacity high-pressure dense lithium iron phosphate prepared in comparative example 1.
Fig. 7 is a graph of XRD test results in example 2.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, the present invention shall be described in further detail with reference to the following detailed description and accompanying drawings.
Example 1:
adding 100g of lithium carbonate into 1000ml of water, ball-milling the lithium carbonate in a high-energy ball mill for 1 hour until the particle size reaches 1000nm, then adding 500g of iron phosphate, 25g of lithium carbonate and 35g of glucose, supplementing 1000ml of water, ball-milling the lithium carbonate in the high-energy ball mill for 5 hours until the particle size reaches 200-300 nm, and spray-drying the slurry. Placing the dried powder in a reaction furnace protected by nitrogen, calcining for 30h at 775 ℃, and cooling to room temperature to obtain LiFePO4powder/C material, SEM (FIG. 1) and capacity test (FIG. 2). EDS spot scan (fig. 3), EIS test (fig. 4), from SEM images, LiFePO4 particle size grading, good particle monodispersity, low surface free carbon, low impedance (see EIS test of fig. 4), and small amounts of in-situ coated iron phosphide (see EDS spot scan of fig. 3).
And (2) taking N-methyl pyrrolidone as a solvent, uniformly stirring the powder obtained after sintering, conductive carbon black and polyvinylidene fluoride according to the mass ratio of 90:5:5, coating the mixture on the surface of a clean aluminum foil, and blade-coating the mixture to form a film. After air blast drying, the electrode sheet was punched into a circular sheet with a diameter of 8mm, and further dried in a vacuum oven at 120 ℃ for 6 hours to remove moisture. The prepared electrode plate is used as a working electrode of a half cell, metal lithium is used as a counter electrode, and 1mol/L LiPF is used6Ethylene Carbonate (EC) -dimethyl carbonate (DMC) (the mass ratio of EC and DMC is 1:1) is used as electrolyte, a battery is assembled in a glove box and subjected to charge and discharge tests, the voltage range is 2.0-3.75V, the charge and discharge multiplying power is 0.1C and 1C, and according to the capacity test result: the 0.1C discharge capacity of the product can reach 159mAh/g, and the 1C discharge capacity can reach 145 mAh/g.
Example 2:
adding 5mol LiOHCrushing in universal crusher to 400-500 nm size, and adding 5mol NH4H2PO45mol of FeO100ml, 0.5mol of LiOH, 40g of cane sugar and 20g of citric acid are added into 5L of ethanol and ball-milled for 3 hours on a high-energy ball mill until the particle size reaches 700-800 nm, and then slurry is spray-dried. Placing the dried powder in a reaction furnace protected by argon, calcining for 15h at 800 ℃, and cooling to room temperature to obtain LiFePO4a/C powder material. XRD testing found a lithium phosphate phase (fig. 7).
The battery preparation process was referenced to example 1.
Example 3:
taking 9mol of LiH2PO4Adding the mixture into 5000ml of methanol, ball-milling the mixture for 5 hours on a high-energy ball mill until the granularity reaches 50-100 nm, and then adding 5mol of Fe2O30.5mol of lithium carbonate, 3g of CNT and 30g of stearic acid, and then 1000ml of water are added to be ball-milled for 10 hours on a high-energy ball mill, and after the particle size reaches 100-200 nm, the slurry is spray-dried. Placing the dried powder in a reaction furnace protected by nitrogen, calcining for 35 hours at 700 ℃, and cooling to room temperature to obtain LiFePO4a/C powder material.
Example 4:
taking 1mol of Li2CO3Crushing in a universal crusher until the granularity reaches 9500-10000 nm, and then adding 4mol of FePO4 and 1.2mol of Li2CO3Adding 1000ml of water into 20g of glucose, performing ball milling on the mixture for 5 hours in a high-energy ball mill, and performing spray drying on the slurry after the particle size reaches 700-800 nm. Placing the dried powder in a reaction furnace protected by nitrogen, calcining for 35 hours at 730 ℃, and cooling to room temperature to obtain LiFePO4a/C powder material.
Example 5:
crushing 0.1mol of LiNO3 in a universal crusher until the granularity reaches 100-200 nm, then adding 1mol of FePO4, 1mol of LiNO3 and 10g of glucose, adding 1000ml of hexanediol, ball-milling for 20 hours in a high-energy ball mill until the particle size reaches 50-100 nm, and spray-drying the slurry. Putting the dried powder into a reaction furnace protected by nitrogen, calcining for 15h at 780 ℃, and cooling to room temperature to obtain LiFePO4a/C powder material.
Comparative example 1:
as a comparative example of example 1, there is provided a method for preparing a positive electrode material for a lithium ion battery, comprising the steps of: adding 500g of iron phosphate, 125g of lithium carbonate and 35g of glucose, supplementing 1000ml of water, ball-milling for 5-6 hours on a high-energy ball mill, and spray-drying the slurry after the particle size reaches 100-200 nm. Placing the dried powder in a reaction furnace protected by nitrogen, calcining the powder for 30 hours at 750 ℃, and cooling the powder to room temperature to obtain LiFePO4powder/C material, SEM (FIG. 5) and capacity test (FIG. 6).
And (2) taking N-methyl pyrrolidone as a solvent, uniformly stirring the powder obtained after sintering, conductive carbon black and polyvinylidene fluoride according to the mass ratio of 90:5:5, coating the mixture on the surface of a clean aluminum foil, and blade-coating the mixture to form a film. After air blast drying, the electrode sheet was punched into a circular sheet with a diameter of 8mm, and further dried in a vacuum oven at 120 ℃ for 6 hours to remove moisture. The prepared electrode plate is used as a working electrode of a half cell, metal lithium is used as a counter electrode, and 1mol/L LiPF is used6Ethylene Carbonate (EC) -dimethyl carbonate (DMC) (the mass ratio of EC to DMC is 1:1) is used as electrolyte, a battery is assembled in a glove box, and the battery is subjected to charge and discharge tests, wherein the voltage range is 2.0-3.75V, and the charge and discharge multiplying power is 0.1C and 1C.
Comparative example 2:
as a comparative example of example 2, there is provided a method of preparing a positive electrode material for a lithium ion battery, comprising the steps of
Taking 5mol of NH4H2PO45mol of FeO100ml, 5.5mol of LiOH, 40g of cane sugar and 20g of citric acid are added into 5L of ethanol and ball-milled for 3 hours on a high-energy ball mill until the particle size reaches 600-700 nm, and then slurry is spray-dried. Placing the dried powder in a reaction furnace protected by argon, calcining for 15h at 800 ℃, and cooling to room temperature to obtain LiFePO4a/C powder material.
The battery preparation process was referenced to comparative example 1.
Comparative example 3:
as a comparative example of example 3, there is provided a method of preparing a positive electrode material for a lithium ion battery, comprising the steps of
Taking 5mol of Fe2O30.5mol of lithium carbonate and 9mol of LiH2PO43g of CNT and 30g of stearic acid, then 5000mL of methanol and 1000mL of water are added for ball milling for 10-11 h in a high-energy ball mill, the particle size reaches 100-200 nm, and then the slurry is sprayed and dried. Placing the dried powder in a reaction furnace protected by nitrogen, calcining for 35 hours at 700 ℃, and cooling to room temperature to obtain LiFePO4a/C powder material.
The battery preparation process was referenced to comparative example 1.
The positive electrode materials prepared in the above examples and comparative examples were fabricated into electrode sheets and batteries, and were subjected to battery performance tests, and the obtained test data are shown in table 1.
TABLE 1 Battery Performance test data
| Numbering | Compacted density (g/cm) of electrode slice3) | 0.1C/0.1C(mAh/g) | 1C/1C(mAh/g) |
| Example 1 | 2.53 | 163.1/159.0 | 145.1/145.1 |
| Example 2 | 2.50 | 162.0/158.9 | 147.1/147.0 |
| Example 3 | 2.60 | 164.2/156.5 | 143.0/143.0 |
| Comparative example 1 | 2.40 | 161.0/157.0 | 144.0/144.0 |
| Comparative example 2 | 2.36 | 158.0/159.0 | 146.0/146.0 |
| Comparative example 3 | 2.47 | 162.9/156.7 | 141.2/141.1 |
As can be seen from table 1, the electrode sheet and the battery fabricated using the positive electrode materials of the above examples of the present invention can maintain a higher discharge capacity while increasing the compacted density, as compared to the comparative examples.
Although specific embodiments of the invention have been disclosed for illustrative purposes and the accompanying drawings, which are included to provide a further understanding of the invention and are incorporated by reference, those skilled in the art will appreciate that: various substitutions, changes and modifications are possible without departing from the spirit and scope of the present invention and the appended claims. The present invention should not be limited to the disclosure of the preferred embodiments and drawings, but should be defined only by the scope of the appended claims.
Claims (10)
1. A preparation method of a high-capacity high-pressure-density lithium battery positive electrode material comprises the following steps:
1) adding a part of lithium salt into a solvent, and grinding or crushing the lithium salt to a certain particle size;
2) mixing another part of lithium salt, a phosphorus source, an iron source and a conductive agent with the lithium salt in the step 1), adding a certain amount of solvent for grinding, and drying to obtain a precursor;
3) sintering the precursor obtained in the step 2) under the protection of inert atmosphere to obtain the lithium battery anode material containing the fast ion conductor compound.
2. The method of claim 1, wherein the lithium salt is ground or crushed to 50 to 10000nm in step 1); and 2) grinding in a ball mill to 50-800 nm.
3. The method of claim 1, wherein the lithium salt in step 1) accounts for 5% to 95% of the total amount of the lithium salt.
4. The method of claim 1, wherein the lithium salt in step 1) and step 2) comprises: one or more of lithium carbonate, lithium dihydrogen phosphate, lithium hydroxide, lithium oxalate, lithium formate, lithium silicate, lithium laurate, lithium malate and lithium citrate.
5. The method of claim 1, wherein the phosphorus source in step 2) is one or more of monoammonium phosphate, diammonium phosphate, lithium dihydrogen phosphate, phosphoric acid, ferric phosphate, pyrophosphoric acid, ferric pyrophosphate, ferric phosphate dihydrate.
6. The method of claim 1, wherein the iron source of step 2) is one or more of iron phosphate, ferrous pyrophosphate, ferric pyrophosphate, ferrous oxide, ferric oxide, basic ferric oxide, ferroferric oxide, ferric phosphate dihydrate.
7. The method of claim 1, wherein the conductive agent in step 2) comprises: one or more of acetylene black, graphite, citric acid, ascorbic acid, sucrose, glucose, cellulose, phenolic resin, CNT, adipic acid, PEG, stearic acid, lauric acid.
8. The method of claim 1, wherein step 3) comprises sintering at 730-800 ℃ for 20-40 hours.
9. The method of claim 1, wherein the fast ion conductor compound of step 3) is Fe2P、FeP、Fe3P、Li3PO4、Li4P2O7One or more of.
10. A high capacity, high pressure dense lithium battery positive electrode material prepared by the method of any one of claims 1 to 9.
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| CN113830747A (en) * | 2021-09-17 | 2021-12-24 | 湖北亿纬动力有限公司 | Low-temperature starting type lithium iron phosphate cathode material and preparation method thereof |
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| CN101559935A (en) * | 2009-05-26 | 2009-10-21 | 华南理工大学 | Lithium iron phosphate cathode material and preparation method thereof |
| JP2011250868A (en) * | 2010-05-31 | 2011-12-15 | Chiba Inst Of Technology | Biomaterial ceramics consisting of tricalcium phosphate, and its manufacturing method |
| CN106299293A (en) * | 2016-09-13 | 2017-01-04 | 青海泰丰先行锂能科技有限公司 | A kind of preparation method of high power capacity height densification olivine cathode material |
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| CN101559935A (en) * | 2009-05-26 | 2009-10-21 | 华南理工大学 | Lithium iron phosphate cathode material and preparation method thereof |
| JP2011250868A (en) * | 2010-05-31 | 2011-12-15 | Chiba Inst Of Technology | Biomaterial ceramics consisting of tricalcium phosphate, and its manufacturing method |
| CN106299293A (en) * | 2016-09-13 | 2017-01-04 | 青海泰丰先行锂能科技有限公司 | A kind of preparation method of high power capacity height densification olivine cathode material |
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| CN113830747A (en) * | 2021-09-17 | 2021-12-24 | 湖北亿纬动力有限公司 | Low-temperature starting type lithium iron phosphate cathode material and preparation method thereof |
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