CN117712346A - Composite positive electrode material, preparation method thereof, positive electrode plate and energy storage device - Google Patents
Composite positive electrode material, preparation method thereof, positive electrode plate and energy storage device Download PDFInfo
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- CN117712346A CN117712346A CN202311841466.XA CN202311841466A CN117712346A CN 117712346 A CN117712346 A CN 117712346A CN 202311841466 A CN202311841466 A CN 202311841466A CN 117712346 A CN117712346 A CN 117712346A
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- positive electrode
- electrode material
- source
- metal element
- iron phosphate
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 101
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 238000004146 energy storage Methods 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 17
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical class [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 claims abstract description 42
- 239000002184 metal Substances 0.000 claims abstract description 41
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 239000010405 anode material Substances 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims description 38
- 238000002156 mixing Methods 0.000 claims description 18
- 239000011247 coating layer Substances 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 229910052720 vanadium Inorganic materials 0.000 claims description 13
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052727 yttrium Inorganic materials 0.000 claims description 13
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 13
- 229910052726 zirconium Inorganic materials 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 239000011733 molybdenum Substances 0.000 claims description 8
- 229910052758 niobium Inorganic materials 0.000 claims description 8
- 239000010955 niobium Substances 0.000 claims description 8
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 8
- 239000010937 tungsten Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011258 core-shell material Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 13
- 238000012360 testing method Methods 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 25
- 239000003792 electrolyte Substances 0.000 description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 4
- DZKDPOPGYFUOGI-UHFFFAOYSA-N tungsten(iv) oxide Chemical compound O=[W]=O DZKDPOPGYFUOGI-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000005955 Ferric phosphate Substances 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229960002380 dibutyl phthalate Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 229940032958 ferric phosphate Drugs 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- LDPWMGUFXYRDRG-UHFFFAOYSA-I niobium(5+) pentaacetate Chemical compound [Nb+5].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O LDPWMGUFXYRDRG-UHFFFAOYSA-I 0.000 description 2
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 2
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229940105963 yttrium fluoride Drugs 0.000 description 2
- QVOIJBIQBYRBCF-UHFFFAOYSA-H yttrium(3+);tricarbonate Chemical compound [Y+3].[Y+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QVOIJBIQBYRBCF-UHFFFAOYSA-H 0.000 description 2
- RBORBHYCVONNJH-UHFFFAOYSA-K yttrium(iii) fluoride Chemical compound F[Y](F)F RBORBHYCVONNJH-UHFFFAOYSA-K 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 2
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 2
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 2
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 229920006184 cellulose methylcellulose Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
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 composite positive electrode material and a preparation method thereof, a positive electrode plate and an energy storage device. And adopting a high-valence metal element M to dope the modified lithium iron phosphate material, and coating the small-size doped modified lithium iron phosphate material to prepare the composite anode material.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a composite positive electrode material, a preparation method thereof, a positive electrode plate and an energy storage device.
Background
In the prior art, lithium iron phosphate (LiFePO 4 LFP) positive electrode materials have been widely used in the fields of mobile power supplies, electric tools, electric automobiles, and energy storage. Compared with other positive electrode materials, the cathode material has the advantages of high energy density, better structural stability and cycle stability, but has the defects of more side reactions with electrolyte, unstable structure and the like, thereby causing poor structural and thermal stability.
Therefore, how to improve the performance of lithium iron phosphate cathode materials is a problem that needs to be solved in the prior art.
Disclosure of Invention
In order to solve the problems of the prior art, the invention provides a composite positive electrode material, which comprises a first positive electrode material and a second positive electrode material;
the first positive electrode material is lithium iron phosphate doped with a metal element M;
the second positive electrode material is in a core-shell structure and comprises an inner core and a coating layer; wherein the inner core is metal element M doped lithium iron phosphate, and the coating layer is one or more of fluoride, oxide and phosphate;
the particle size of the first positive electrode material is larger than that of the inner core;
the metal element M is one or more of titanium, vanadium, niobium, molybdenum, tungsten, zirconium and yttrium.
According to one embodiment of the invention, the metal element M is one or more of titanium, vanadium, zirconium and yttrium.
According to one embodiment of the invention, the particle size of the inner core is in the range of 50nm to 500nm, preferably 300nm to 500nm, more preferably 400nm to 500nm; the particle size of the first positive electrode material ranges from 1000nm to 3000nm, preferably from 1000nm to 2000nm.
According to one embodiment of the invention, the metal element M is one or more of titanium, vanadium, zirconium and yttrium.
According to one embodiment of the invention, the mass ratio of the first positive electrode material to the second positive electrode material is 1:1-1:4.
According to a specific embodiment of the present invention, in the first positive electrode material, the doping amount of the metal element M is 500ppm to 4000ppm, preferably 500ppm to 3000ppm; and/or the number of the groups of groups,
in the core of the second positive electrode material, the doping amount of the metal element M is 500ppm to 4000ppm, preferably 500ppm to 3000ppm.
According to one embodiment of the present invention, the thickness of the coating layer is 1nm to 3nm, and may be 1nm, 2nm, or 3nm.
The second object of the present invention is to provide a preparation method of the above composite positive electrode material, which specifically includes the following steps:
(1) Mixing and roasting a phosphorus source, an iron source, a lithium source, a metal element M precursor and a carbon source to obtain lithium iron phosphate subjected to metal element M doping modification;
(2) Crushing the metal element M doped and modified lithium iron phosphate obtained in the step (1) to obtain a first anode material and a core;
(3) Uniformly mixing the coating precursor and the inner core, ball milling and roasting to obtain a second anode material;
(4) And uniformly mixing the first positive electrode material and the second positive electrode material to obtain the composite positive electrode material.
According to an embodiment of the present invention, in the step (1), the metal element M precursor is one or more of a titanium source, a niobium source, a vanadium source, a zirconium source, an yttrium source, a tungsten source, and a molybdenum source.
According to a specific embodiment of the invention, the titanium source is selected from one or more of meta-titanic acid, titanium dioxide, butyl phthalate; and/or the number of the groups of groups,
the niobium source is selected from one or more of niobium pentoxide, niobium oxalate and niobium acetate; and/or the number of the groups of groups,
the vanadium source is one or more selected from ammonium metavanadate, vanadium pentoxide, vanadium dioxide, vanadium oxide and vanadyl oxalate; and/or the number of the groups of groups,
the zirconium source is selected from one or more of zirconium oxide, zirconium fluoride, zirconium hydroxide, zirconium carbonate and zirconium phosphate; and/or the number of the groups of groups,
the yttrium source is selected from one or more of yttrium oxide, yttrium fluoride and hydrated yttrium carbonate; and/or the number of the groups of groups,
the tungsten source is selected from one or more of tungsten dioxide and tungsten trioxide; and/or the number of the groups of groups,
the molybdenum source is selected from one or more of molybdenum dioxide and molybdenum trioxide.
According to an embodiment of the present invention, in the step (1), the baking atmosphere is an inert atmosphere; the roasting temperature is 600-900 ℃; the roasting time is 5-10 h.
According to an embodiment of the present invention, in the step (1), the carbon source is added in an amount of 0.5wt% to 5wt%.
The third object of the invention is to provide a positive electrode plate, which comprises the positive electrode material or the positive electrode material prepared by the preparation method.
A fourth object of the present invention is to provide an energy storage device comprising: the positive electrode material or the positive electrode material prepared by the preparation method or the positive electrode plate.
According to an embodiment of the present invention, the energy storage device is a lithium ion battery.
Drawings
FIG. 1 is a DSC test curve of examples 1-4 and comparative example 1;
fig. 2 is a TEM image of the coated and modified lithium iron phosphate in example 1 (left) and example 4 (right);
FIG. 3 shows the discharge rate capacity retention at 25℃and 0.5P for examples 1-4 and comparative example 1;
FIG. 4 shows the cycle performance graphs of examples 1-5 and comparative example 1 at 25℃and 0.5P;
FIG. 5 shows the cycle performance at 45℃and 1P for examples 1-5 and comparative example 1.
Detailed Description
The inventors have found that blending with particles of different sizes is currently the dominant way to improve the compacted density and processing characteristics of lithium iron phosphate. Although lithium iron phosphate has good structural stability and cycling stability in many positive electrode materials, the large-size lithium iron phosphate positive electrode active material with the particle diameter of more than 1000nm is easy to generate particle breakage or pulverization in the cycling process, and the mechanical integrity of the positive electrode active material particles is reduced, so that active material loss and electrochemical performance attenuation are caused. In addition, the small-sized lithium iron phosphate positive electrode active material with the particle size smaller than 500nm is very easy to generate side reaction with electrolyte due to higher particle surface activity, thereby causing capacity loss.
In view of this, the present invention provides a composite positive electrode material including a first positive electrode material and a second positive electrode material;
the first positive electrode material is lithium iron phosphate doped with a metal element M;
the second positive electrode material is in a core-shell structure and comprises an inner core and a coating layer; wherein the inner core is metal element M doped lithium iron phosphate, and the coating layer is one or more of fluoride, oxide and phosphate;
the particle size of the first positive electrode material is larger than that of the inner core;
the metal element M is one or more of titanium, vanadium, niobium, molybdenum, tungsten, zirconium and yttrium.
According to one embodiment of the invention, the metal element M is one or more of titanium, vanadium, zirconium and yttrium.
In order to improve the cycle stability and the thermal stability of the lithium iron phosphate positive electrode material, the invention adopts a high-valence metal M doped modified lithium iron phosphate material, and carries out coating treatment on small-size doped modified lithium iron phosphate, thereby preparing the composite positive electrode material. On the one hand, the high-valence metal element is doped and modified at the iron site to form a hole type semiconductor so as to improve the conductivity of the positive electrode material and reduce the moving resistance of electrons in the positive electrode material, in addition, the doping and modification is also beneficial to the generation of lithium vacancies, the intercalation and deintercalation of lithium ions are facilitated, the efficiency of transmitting lithium ions by the positive electrode material is improved, and the conductivity and the cycle performance of the positive electrode material when the positive electrode material is applied to a positive electrode plate are further improved. On the other hand, the coating modification of the small-size lithium iron phosphate material can inhibit the reaction between the small-size lithium iron phosphate material and the electrolyte in the circulation process, improve the initial temperature of the reaction between the electrolyte and the positive electrode material after lithium removal, reduce the reaction heat value, and improve the lattice stability of the material and the interface stability of the positive electrode and the electrolyte. The two means act cooperatively, thus improving the capacity retention rate, the battery capacity and the thermal stability.
The cycling stability and the thermal stability of the lithium iron phosphate can be improved by mixing the large particles with the small particles with the coating layer according to a certain proportion, compared with the technical scheme that the large particles and the small particles are provided with the coating layer, the defects that the polarization of the large particles is large, the capacity is poor, the conductivity of the coating is poor, and the electrochemical performance of the coating is further reduced are overcome.
The high-valence metal element M is adopted to carry out doping modification on the lithium iron phosphate, and compared with other metal elements, the single doping and the mixed doping of the element M can improve the oxygen dissociation energy of the lithium iron phosphate/ferric phosphate, so that the thermal stability is improved.
Fluoride, oxide and phosphate are selected as coating interface layers, so that on one hand, side reactions of the positive electrode material and electrolyte in the circulation process can be inhibited, and on the other hand, the conductivity and the circulation performance of the positive electrode plate can be improved.
According to one embodiment of the invention, the particle size of the inner core is in the range of 50nm to 500nm, preferably 300nm to 500nm, more preferably 400nm to 500nm; the particle size of the first positive electrode material ranges from 1000nm to 3000nm, preferably from 1000nm to 2000nm.
According to the invention, by adjusting the particle sizes of the inner core and the first positive electrode material within the range, if the particle size of the inner core is smaller than 50nm, the coating layer is too thick, the reactivity is seriously reduced, the inner core size is larger than 500nm, the reaction kinetic activity is reduced, the rate performance is reduced, the lithium ion intercalation and deintercalation rate is further reduced by the coating layer, and the reversible capacity is reduced; the particle size of the first positive electrode material is larger than 3000nm, capacity exertion is obviously reduced, and the first positive electrode material is not suitable for preparing electrodes.
According to one embodiment of the invention, the metal element M is one or more of titanium, vanadium, zirconium and yttrium.
According to one embodiment of the invention, the mass ratio of the first positive electrode material to the second positive electrode material is 1:1-1:4.
By controlling the mass ratio of the first positive electrode material to the second positive electrode material within the above range, the first positive electrode material occupies too little space, the hole semiconductor and lithium vacancy in the composite positive electrode material are less, the lithium ion transmission efficiency is poor, and the cycle life can be remarkably reduced; the first positive electrode material has an excessive ratio, and the lattice stability of the composite positive electrode material and the interface stability between the composite positive electrode material and the electrolyte are reduced, so that the rate performance is reduced.
According to a specific embodiment of the present invention, in the first positive electrode material, the doping amount of the metal element M is 500ppm to 4000ppm, preferably 500ppm to 3000ppm; and/or the number of the groups of groups,
in the core of the second positive electrode material, the doping amount of the metal element M is 500ppm to 4000ppm, preferably 500ppm to 3000ppm.
The lattice stability can be improved by doping and modifying the lithium iron phosphate. When the doping amount is less than 500ppm, the modification effect is not obvious; when the total amount of doping is more than 3000ppm, the improvement of the overall performance is not obvious any more. When the total doping amount is more than 4000ppm, the electrochemical performance is affected, small particles are increased in the synthesis process, and the polar allocation of the large particles is uncontrollable.
According to one embodiment of the present invention, the thickness of the coating layer is 1nm to 3nm, and may be 1nm, 2nm, or 3nm.
The small-particle lithium iron phosphate is coated, so that the small-particle lithium iron phosphate can be prevented from reacting with electrolyte; however, when the thickness exceeds 3nm, the kinetics of small particles are drastically attenuated, resulting in a decrease in capacity.
The second object of the present invention is to provide a preparation method of the above composite positive electrode material, which specifically includes the following steps:
(1) Mixing and roasting a phosphorus source, an iron source, a lithium source, a metal element M precursor and a carbon source to obtain lithium iron phosphate subjected to metal element M doping modification;
(2) Crushing the metal element M doped and modified lithium iron phosphate obtained in the step (1) to obtain a first anode material and a core;
(3) Uniformly mixing the coating precursor and the inner core, ball milling and roasting to obtain a second anode material;
(4) And uniformly mixing the first positive electrode material and the second positive electrode material to obtain the composite positive electrode material.
According to an embodiment of the present invention, in the step (1), the metal element M precursor is one or more of a titanium source, a niobium source, a vanadium source, a zirconium source, an yttrium source, a tungsten source, and a molybdenum source.
According to a specific embodiment of the invention, the titanium source is selected from one or more of meta-titanic acid, titanium dioxide, butyl phthalate; and/or the number of the groups of groups,
the niobium source is selected from one or more of niobium pentoxide, niobium oxalate and niobium acetate; and/or the number of the groups of groups,
the vanadium source is one or more selected from ammonium metavanadate, vanadium pentoxide, vanadium dioxide, vanadium oxide and vanadyl oxalate; and/or the number of the groups of groups,
the zirconium source is selected from one or more of zirconium oxide, zirconium fluoride, zirconium hydroxide, zirconium carbonate and zirconium phosphate; and/or the number of the groups of groups,
the yttrium source is selected from one or more of yttrium oxide, yttrium fluoride and hydrated yttrium carbonate; and/or the number of the groups of groups,
the tungsten source is selected from one or more of tungsten dioxide and tungsten trioxide; and/or the number of the groups of groups,
the molybdenum source is selected from one or more of molybdenum dioxide and molybdenum trioxide.
According to an embodiment of the present invention, in the step (1), the baking atmosphere is an inert atmosphere; the roasting temperature is 600-900 ℃; the roasting time is 5-10 h.
According to an embodiment of the present invention, in the step (1), the carbon source is added in an amount of 0.5wt% to 5wt%.
The third object of the invention is to provide a positive electrode plate, which comprises the positive electrode material or the positive electrode material prepared by the preparation method.
A fourth object of the present invention is to provide an energy storage device comprising: the positive electrode material or the positive electrode material prepared by the preparation method or the positive electrode plate.
According to an embodiment of the present invention, the energy storage device is a lithium ion battery.
Example 1
(1) Preparation of cathode Material
Weighing 378.69g of lithium carbonate, 1508.2g of ferric phosphate and 1.597g of titanium dioxide, mixing in deionized water, adding 3wt% of active carbon into the mixture, and performing mixing and particle size regulation through ball milling and sand milling; after the slurry is spray-dried, presintering for 3 hours at 350 ℃ in an atmosphere furnace in nitrogen atmosphere, then sintering for 8 hours at 800 ℃, and crushing powder after sintering is completed; crushing, mixing large particle lithium iron phosphate with particle size of 1000-3000 nm and small particle lithium iron phosphate with particle size of 50-500 nmSeparately collected, 0.2% wt Al was used 2 O 3 And after uniformly mixing the coating precursor and the small particles, sintering the mixture for 2 hours in an inert atmosphere at 500 ℃ to obtain the coated and modified small-particle lithium iron phosphate. And finally mixing large-particle lithium iron phosphate and small-particle lithium iron phosphate in a mass ratio of (1:1) to obtain the lithium iron phosphate positive electrode material of the example 1.
Examples 2 to 5
Other conditions were the same as in example 1 except that the metal element M precursor, the coating precursor, and the mass ratio of the large and small particles were different, and specific parameters are shown in Table 1.
Comparative example 1
Other conditions were the same as in example 1 except that the metal element M precursor was not added and the subsequent breakage, sieving, and coating processes were not performed, and specific parameters are shown in table 1.
(2) Preparation of positive pole piece
The positive electrode material obtained in the embodiment is applied to preparation of a positive electrode plate, the positive electrode material, a conductive agent (conductive carbon black, SP) and a binder (polyvinylidene fluoride, PVDF) are dispersed in an N-methyl pyrrolidone (NMP) solution according to the mass ratio of 80:10:10, positive electrode slurry is obtained through uniform mixing, the positive electrode slurry is coated on a positive electrode current collector layer (aluminum foil) to form a positive electrode material layer, and the positive electrode plate is obtained after drying, cold pressing, slitting and cutting.
(3) Preparation of negative pole piece
Dispersing graphite, a conductive agent (conductive carbon black, SP) and a binder (sodium carboxymethylcellulose, CMC) in water according to a certain mass ratio, uniformly mixing to obtain negative electrode slurry, coating the negative electrode slurry on a negative electrode current collector layer (copper foil) to form a negative electrode material layer, and drying, cold pressing, slitting and cutting to obtain a negative electrode plate.
(4) Diaphragm
A polypropylene film was used as a separator.
(5) Preparation of electrolyte
A certain amount of lithium hexafluorophosphate (LiPF 6) was dissolved as an electrolyte in a solution prepared from methyl ethyl carbonate (EMC) and Ethylene Carbonate (EC) at a volume ratio of 7:3, and the concentration of lithium hexafluorophosphate was 1.0M.
And assembling the positive pole piece, the negative pole piece, the diaphragm and the electrolyte into the lithium ion battery.
(6) Characterization of materials and performance testing
The positive electrode material is subjected to thermal stability test and morphology characterization, and the specific method is as follows:
(1) thermal stability test:
the thermal stability of the positive electrode material was tested by Differential Scanning Calorimetry (DSC), and the specific operation is as follows: and (3) placing the prepared test battery on a test cabinet (5V, 10 mA) for constant-power charge-discharge capacity test, setting the test temperature to 25 ℃, setting the first-round charge multiplying power to 0.1C, and charging the test battery to the voltage of 4.2V of the test battery, and then charging the test battery to 0.02C by using the constant voltage. In a glove box, disassembling the test battery in an overcharged state, collecting and weighing a certain mass of positive electrode material, dripping a certain proportion of electrolyte, then filling the electrolyte into a platinum crucible, and testing the positive electrode material in a delithiated state through a differential scanning calorimeter.
(2) Morphology characterization:
the morphology of the positive electrode material was observed using a Transmission Electron Microscope (TEM). Sample preparation operation: and dispersing the lithium iron phosphate powder in an ethanol solution and performing ultrasonic treatment. The ultrasonic sample is uniformly dispersed on a copper mesh (phi=3mm) with a supporting film, and is tested, the model of a transmission electron microscope is FEI Titan Themis TEM, the magnification is 50-200 ten thousand times, and the test conditions are as follows: the accelerating voltage is 60-300kV.
The electrochemical performance test of the lithium ion battery is carried out, and the specific test method is as follows:
(1) and (3) multiplying power performance test: and carrying out constant power charge-discharge capacity test on the prepared part of test batteries and part of comparison batteries on a test cabinet (5V, 10 mA), wherein the power is respectively set to be 0.25P, 0.5P, 1P and 2P, and respectively collecting the 0.25P discharge capacity, the 0.5P discharge capacity, the 1P discharge capacity and the 2P discharge capacity of the test batteries and the comparison batteries.
(2) 25 ℃ cycle performance test: the prepared test battery and the prepared comparative battery are subjected to constant-power charge-discharge capacity test on a test cabinet (5V, 10 mA), and the specific operation is as follows: the test temperature was set at 25 ℃, the charge and discharge rate was set at 0.5P (i.e., both charge and discharge rates were 0.5P), the voltage interval was 2.5V to 3.75V, and 0.5P discharge capacity data for different cycles was collected.
(3) 45 ℃ cycle performance test: the prepared test battery and the prepared comparative battery are subjected to constant-power charge-discharge capacity test on a test cabinet (5V, 10 mA), and the specific operation is as follows: the test temperature is set to 25 ℃, the charge-discharge multiplying power is set to 1P (namely, the charge multiplying power and the discharge multiplying power are both 1P), the voltage interval is 2.5V to 3.75V, and 1P discharge capacity data of different cycle numbers are collected.
Table 1 table of preparation parameters of examples 1 to 5 and comparative example 1
TABLE 2 data sheets of the main reaction exotherm and total exotherm for examples 1-4 and comparative example 1
The main exothermic heat of reaction and the total exothermic spectra of examples 1 to 4 and comparative example 1 are shown in table 2, and it can be seen that the cathode material of comparative example 1 has significantly higher heat of reaction than those of examples 1 to 4, and that the total exothermic heat of reaction of comparative example 1 is much higher than those of examples 1 to 4, although the deoxidizing exothermic heat of comparative example 1 is lower than those of examples 2 to 4. Therefore, the technical means of the invention is adopted, the high-valence metal M is adopted to dope the modified lithium iron phosphate material, and the small-size doped modified lithium iron phosphate is coated, so that the thermal stability of the lithium iron phosphate material can be improved.
The DSC test curves of examples 1 to 4 and comparative example 1 are shown in fig. 1, and it can be seen that the heat flow of the cathode material of comparative example 1 is significantly higher than that of examples 1 to 4, and the heat initiation temperature of the cathode material of comparative example 1 is significantly lower than that of examples 1 to 4. Therefore, the technical means of the invention is adopted, the high-valence metal M is adopted to dope the modified lithium iron phosphate material, and the small-size doped modified lithium iron phosphate is coated, so that the thermal stability of the lithium iron phosphate material can be improved, and the thermal initiation temperature of the positive electrode material can be reduced.
TEM images of the coated modified lithium iron phosphate in example 1 (left) and example 4 (right) are shown in FIG. 2. It can be seen that, as Al 2 O 3 The coating amount is increased, and the coating layer is thickened. As can be seen in conjunction with fig. 1 and 2, the thermal stability of the lithium iron phosphate material increases as the coating layer increases.
As can be seen from fig. 3, the discharge rate-capacity retention rates of examples 1 to 4 and comparative example 1 at 25 ℃ on the basis of 0.5P are all better than those of comparative example 1, and the capacity retention rates of examples 3 and 4 are significantly improved as can be seen from fig. 3.
The discharge rate-capacity test results of the pouch cells of examples 1 to 4 and comparative example 1 having a battery capacity of 2.7Ah are shown in table 3:
table 3 discharge rate-capacity test performance data of examples 1 to 4 and comparative example 1
As can be seen from table 3, the battery capacities of examples 1 to 4 were all greater than comparative example 1 under discharge rates of 0.25P, 0.5P, 1P, and 2P. The cycle performance diagrams of examples 1 to 5 and comparative example 1 at 25℃and 0.5P are shown in FIG. 4, and the battery capacity of comparative example 1 at 25℃and 0.5P is significantly lower than that of examples 1 to 5. The cycle performance diagrams of examples 1 to 5 and comparative example 1 at 45℃and 1P are shown in FIG. 5, and the battery capacity of comparative example 1 at 45℃and 1P is significantly lower than that of examples 1 to 5. Therefore, the technical means of the invention is adopted, the high-valence metal M is adopted to dope the modified lithium iron phosphate material, and the small-size doped modified lithium iron phosphate is coated, so that the battery capacity of the positive electrode material can be improved.
Unless otherwise defined, all terms used herein are intended to have the meanings commonly understood by those skilled in the art.
The described embodiments of the present invention are intended to be illustrative only and not to limit the scope of the invention, and various other alternatives, modifications, and improvements may be made by those skilled in the art within the scope of the invention, and therefore the invention is not limited to the above embodiments but only by the claims.
Claims (10)
1. A composite positive electrode material, characterized in that the composite positive electrode material comprises a first positive electrode material and a second positive electrode material;
the first positive electrode material is lithium iron phosphate doped with a metal element M;
the second anode material is in a core-shell structure and comprises an inner core and a coating layer; the inner core is lithium iron phosphate doped with metal element M, and the coating layer is one or more of fluoride, oxide and phosphate;
the particle size of the first positive electrode material is larger than that of the inner core;
the metal element M is one or more of titanium, vanadium, niobium, molybdenum, tungsten, zirconium and yttrium; preferably, the metal element M is one or more of titanium, vanadium, zirconium and yttrium.
2. The positive electrode material according to claim 1, wherein the particle diameter of the core ranges from 50nm to 500nm; the particle size range of the first positive electrode material is 1000 nm-3000 nm.
3. The positive electrode material according to claim 1, wherein a mass ratio of the first positive electrode material to the second positive electrode material is 1:1 to 1:4.
4. The positive electrode material according to claim 1, wherein in the first positive electrode material, the doping amount of the metal element M is 500ppm to 4000ppm, preferably 500ppm to 3000ppm; and/or the number of the groups of groups,
in the core of the second positive electrode material, the doping amount of the metal element M is 500ppm to 4000ppm, preferably 500ppm to 3000ppm.
5. The positive electrode material according to claim 1, wherein the thickness of the coating layer is 1nm to 3nm.
6. The method for preparing a positive electrode material according to any one of claims 1 to 5, comprising the steps of:
(1) Mixing and roasting a phosphorus source, an iron source, a lithium source, a metal element M precursor and a carbon source to obtain lithium iron phosphate subjected to metal element M doping modification;
(2) Crushing the metal element M doped and modified lithium iron phosphate obtained in the step (1) to obtain the first anode material and the inner core;
(3) Uniformly mixing the coating precursor and the inner core, ball milling and roasting to obtain the second anode material;
(4) And uniformly mixing the first positive electrode material and the second positive electrode material to obtain the composite positive electrode material.
7. The method according to claim 6, wherein in the step (1), the metal element M precursor is one or more of a titanium source, a niobium source, a vanadium source, a zirconium source, an yttrium source, a tungsten source, and a molybdenum source.
8. The method according to claim 6, wherein the carbon source is added in an amount of 0.5 to 5wt% in the step (1).
9. A positive electrode sheet, characterized by comprising: the positive electrode material according to any one of claims 1 to 5, or the positive electrode material produced by the method according to any one of claims 6 to 8.
10. An energy storage device, comprising: the positive electrode material according to any one of claims 1 to 5, or the positive electrode material produced by the method according to any one of claims 6 to 8, or the positive electrode sheet according to claim 9.
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