CN102420322B - Multielement composite cathode material for lithium secondary battery and preparation method thereof - Google Patents
Multielement composite cathode material for lithium secondary battery and preparation method thereof Download PDFInfo
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- CN102420322B CN102420322B CN2011103693164A CN201110369316A CN102420322B CN 102420322 B CN102420322 B CN 102420322B CN 2011103693164 A CN2011103693164 A CN 2011103693164A CN 201110369316 A CN201110369316 A CN 201110369316A CN 102420322 B CN102420322 B CN 102420322B
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- secondary battery
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 48
- 239000010406 cathode material Substances 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 27
- 238000001816 cooling Methods 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 238000005245 sintering Methods 0.000 claims abstract description 14
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 12
- 238000012360 testing method Methods 0.000 claims abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 6
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 6
- 239000011574 phosphorus Substances 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 229910052788 barium Inorganic materials 0.000 claims abstract description 4
- 229910052796 boron Inorganic materials 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 229910001947 lithium oxide Inorganic materials 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 23
- 238000013467 fragmentation Methods 0.000 claims description 15
- 238000006062 fragmentation reaction Methods 0.000 claims description 15
- 238000012216 screening Methods 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 13
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 12
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 12
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 5
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019838 diammonium phosphate Nutrition 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
- 239000000203 mixture Substances 0.000 claims description 3
- 238000012956 testing procedure Methods 0.000 claims description 3
- 230000001427 coherent effect Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 150000003839 salts Chemical group 0.000 claims description 2
- 238000002050 diffraction method Methods 0.000 claims 1
- 150000007522 mineralic acids Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 24
- 238000005303 weighing Methods 0.000 abstract description 10
- 238000002156 mixing Methods 0.000 abstract description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 229940126062 Compound A Drugs 0.000 abstract 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 abstract 2
- 238000007873 sieving Methods 0.000 abstract 2
- 229910003618 NixCoyMn1-x-y(OH)2 Inorganic materials 0.000 abstract 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 80
- 239000011572 manganese Substances 0.000 description 54
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 19
- 102220043159 rs587780996 Human genes 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 9
- 238000002479 acid--base titration Methods 0.000 description 8
- 238000009413 insulation Methods 0.000 description 8
- 229910020632 Co Mn Inorganic materials 0.000 description 7
- 229910020678 Co—Mn Inorganic materials 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 239000011149 active material Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 3
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 3
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 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
- 239000005030 aluminium foil Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- GBCAVSYHPPARHX-UHFFFAOYSA-M n'-cyclohexyl-n-[2-(4-methylmorpholin-4-ium-4-yl)ethyl]methanediimine;4-methylbenzenesulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1.C1CCCCC1N=C=NCC[N+]1(C)CCOCC1 GBCAVSYHPPARHX-UHFFFAOYSA-M 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A multielement composite cathode material for a lithium secondary battery and a preparation method thereof. The chemical formula of the multielement composite cathode material for a lithium secondary battery is LiaNixCoyMn1-x-yMzO2(PO4)b, wherein M is selected from one or two elements of Mg, Al, Zr, Ba. Sr and B; 0.8<=a<=1.2; 0<x<1; 0<y<1; x+y<=1; 0.0005<=z<=0.02; 0<b<=0.02. The preparation method comprises the following steps: weighing NixCoyMn1-x-y(OH)2, lithium salts or lithium oxide or lithium hydroxide, and compounds containing the element M, mixing, sintering at 700-950 DEG C for 6-24 hours, cooling, crushing, sieving to obtain a compound A expressed as LiaNixCoyMn1-x-yMzO2; testing residual lithium element content of the compound A, adding a phosphorus-containing compound, performing heat treatment at 300-900 DEG C for 2-10 hours, cooling, crushing, and sieving. The multielement composite cathode material for a lithium secondary battery has good cycle performance, and low expansion; a cathode of a lithium secondary battery prepared by the material has good working performance.
Description
Technical field
The present invention relates to a kind of anode materials for lithium secondary cells and preparation method thereof, especially relate to a kind of multielement composite cathode material for lithium secondary battery and preparation method thereof.
Background technology
Nickle cobalt lithium manganate is the anode material for lithium-ion batteries of ternary doping, combines LiCoO
2, LiNiO
2With
m-LiMnO
2The characteristics of three kinds of stratified materials, its performance are better than above arbitrary one-component positive electrode, have obvious trielement synergistic effect: by introducing Co, can reduce cation mixing occupy-place situation, effectively the layer structure of stabilizing material; By introducing Ni, can improve the capacity of material; By introducing Mn, not only can reduce material cost, but also can improve the fail safe of material.This material basic physical properties and charge and discharge platform and LiCoO
2Close, be suitable for existing all kinds of lithium ion battery applications products, be expected to replace existing LiCoO
2Positive electrode.
At present, in order to make nickle cobalt lithium manganate, have more superiority, be applied on electrokinetic cell and automobile batteries, nickel-cobalt lithium manganate cathode material cycle performance and high temperature inflatable performance need further improve.CN 101630736A discloses a kind of improving one's methods of nickel-cobalt-manganese ternary positive electrode cycle performance of improving, and first tertiary cathode material is detected to analysis, obtains the lithium carbonate residual volume, according to lithium carbonate residual volume proportioning, adds TiO
2, high temperature less than 900 ℃ under reaction obtain containing Li
2TiO
3Tertiary cathode material.But due to TiO being arranged in reaction
2Introducing, TiO
2Be a kind of more active material, will cause the decomposition of electrolyte, if TiO
2Not thorough with the lithium carbonate reaction of remaining 1000ppm level, will cause containing Li
2TiO
3Tertiary cathode material have the problem of high temperature inflatable.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes the deficiencies in the prior art, and multielement composite cathode material for lithium secondary battery that a kind of good cycle and inflatable are low and preparation method thereof is provided.
The present invention's multielement composite cathode material for lithium secondary battery, its chemical formula are Li
aNi
xCo
yMn
1-x-yM
zO
2(PO
4)
b, for Powdered;
In described chemical formula, M is one or two or more kinds the element that is selected from Mg, Al, Zr, Ba, Sr and B, and a, x, y, z and b are the values of the mol ratio of coherent element, are respectively 0.8≤a≤1.2,0<x<1,0<y<1, x+y≤1,0.0005≤z≤0.02,0<b≤0.02;
Tap density>=the 1.5g/cm of described multielement composite cathode material for lithium secondary battery
3, can increase the amount that is filled into the positive electrode in battery, can make the charge/discharge capacity of every battery unit volume larger.
The preparation method of the present invention's multielement composite cathode material for lithium secondary battery comprises the following steps:
(1) take Ni
xCo
yMn
1-x-y(OH)
2Compound, lithium salts or lithia or the lithium hydroxide of expression, contain the compound of element M, making the Li:Ni:Co:Mn:M stoichiometric proportion is a:x:y:(1-x-y): z, wherein a, x, y, z are respectively 0.8≤a≤1.2,0<x<1,0<y<1, x+y≤1,0.0005≤z≤0.02, mix, then at 700-950 ℃ of (preferred 750 ℃) preferred 20h of sintering 6-24h(), cooling rear fragmentation, screening, obtaining chemical formula is Li
aNi
xCo
yMn
1-x-yM
zO
2The compd A of expression;
(2) the remaining elemental lithium content of testing procedure (1) gained compd A, add the phosphorus-containing compound of Li/P molar ratio>=3, then at 300-900 ℃ of (preferred 800 ℃) preferred 3h of heat treatment 2-10h(), after cooling, fragmentation, screening, namely obtaining chemical formula is Li
aNi
xCo
yMn
1-x-yM
zO
2(PO
4)
bThe multielement composite cathode material for lithium secondary battery of expression.
Described Ni
xCo
yMn
1-x-y(OH)
2Compound tap density>=the 1.0g/cm of expression
3, the average grain diameter D50=5-20 μ m of laser diffraction (Laser diffraction) method test, the shape preferred class of powder particle is spherical;
The described compound that contains element M can be salt, oxide or the hydroxide that contains element M, when M is B, can be boric acid.
The preferred lithium carbonate of described lithium salts.
At least a in described phosphorus-containing compound preferably phosphoric acid ammonium dihydrogen, diammonium hydrogen phosphate, lithium dihydrogen phosphate.
The present invention's multielement composite cathode material for lithium secondary battery, carry out the doping of Mg, Al, Zr, Ba, Sr and B to existing nickle cobalt lithium manganate, further improves the structural stability of material, improves cycle performance and the thermal stability of product; Product surface adopts phosphate treatment; reduce the content of surface carbon hydrochlorate; simultaneously it and nonaqueous electrolyte lithium hexafluoro phosphate compatibility are better; the corrosion of isolated electrolyte to the matrix active material; protect its active material, the high temperature inflatable that makes product have cycle performance preferably and reduce the product lithium secondary battery.The present invention's multielement composite cathode material for lithium secondary battery, good cycle and inflatable are low, with its cathode plate for lithium secondary battery of making, favorable working performance.
The accompanying drawing explanation
Fig. 1 is electronic scanning Electronic Speculum (SEM) photo of nickle cobalt lithium manganate in the embodiment of the present invention 1, amplifies 3000 times;
Fig. 2 is electronic scanning Electronic Speculum (SEM) photo of nickle cobalt lithium manganate in the embodiment of the present invention 2, amplifies 3000 times.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.But shall not be construed as limiting the scope of the invention.
Embodiment 1
The multielement composite cathode material for lithium secondary battery of the present embodiment, its chemical formula are Li
1.08Ni
2/5Co
1/5Mn
2/5Mg
0.01O
2(PO
4)
0.0027, for Powdered.
Its preparation method:
(1) take Ni
2/5Co
1/5Mn
2/5(OH)
2The nickel Co-Mn compound of expression (the average grain diameter D50=10.0 μ m that adopts laser particle analyzer to survey, tap density 2.05g/cm
3, the powder particle class is spherical) and 280.00g and lithium carbonate 122.19g and magnesium carbonate 2.57g, dry type is mixed, is placed in Muffle furnace, then at 900 ℃ of sintering 10h, cooling rear fragmentation, screening, obtaining chemical formula is Li
1.08Ni
2/5Co
1/5Mn
2/5Mg
0.01O
2The compd A of expression;
(2) adopt acid-base titration to record this Li
1.08Ni
2/5Co
1/5Mn
2/5Mg
0.01O
2The remaining elemental lithium content of material is 658ppm, the above-mentioned synthetic Li of weighing 200g
1.08Ni
2/5Co
1/5Mn
2/5Mg
0.01O
2Material, add the ammonium dihydrogen phosphate of 0.62g, and dry mixed, be placed in Muffle furnace, 400 ℃ of insulation 6h, cooling with stove after, crush and screen, obtain nickle cobalt lithium manganate Li
1.08Ni
2/5Co
1/5Mn
2/5Mg
0.01O
2(PO
4)
0.0027.
Gained nickle cobalt lithium manganate Li
1.08Ni
2/5Co
1/5Mn
2/5Mg
0.01O
2(PO
4)
0.0027Tap density is 2.53g/cm
3(adopting the GB/T5162-1985 method to test), adopt electronic scanning Electronic Speculum (SEM) to carry out morphology analysis to product, and its pattern as shown in Figure 1.
Embodiment 2
The multielement composite cathode material for lithium secondary battery of the present embodiment, its chemical formula are Li
1.04Ni
1/2Co
1/5Mn
3/10Zr
0.01O
2(PO
4)
0.0017, for Powdered;
Its preparation method:
(1) take Ni
1/2Co
1/5Mn
3/10(OH)
2The nickel Co-Mn compound of expression (the average grain diameter D50=8.0 μ m that adopts laser particle analyzer to survey, tap density 1.60g/cm
3, powder particle shape class is spherical) and 280.00g, lithium carbonate 116.89g, zirconia 3.74g, dry type is mixed, is placed in Muffle furnace, then at 850 ℃ of sintering 20h, cooling rear fragmentation, screening, obtaining chemical formula is Li
1.04Ni
1/2Co
1/5Mn
3/10Zr
0.01O
2The compd A of expression;
(2) adopt acid-base titration to record this Li
1.04Ni
1/2Co
1/5Mn
3/10Zr
0.01O
2The remaining elemental lithium content of material is 451ppm, the above-mentioned synthetic Li of weighing 200g
1.04Ni
1/2Co
1/5Mn
3/10Zr
0.01O
2Material, add the diammonium hydrogen phosphate of 0.46g, and dry mixed, be placed in Muffle furnace, 600 ℃ of insulation 3h, cooling with stove after, crush and screen, obtain nickle cobalt lithium manganate Li
1.04Ni
1/2Co
1/5Mn
3/10Zr
0.01O
2(PO
4)
0.0017.
Gained nickle cobalt lithium manganate Li
1.08Ni
2/5Co
1/5Mn
2/5Mg
0.01O
2(PO
4)
0.0017Tap density is 2.42g/cm
3(adopting the GB/T5162-1985 method to test), adopt electronic scanning Electronic Speculum (SEM) to the product morphology analysis, and its pattern as shown in Figure 2.
Embodiment 3
The multielement composite cathode material for lithium secondary battery of the present embodiment, its chemical formula are Li
1.12Ni
3/5Co
1/5Mn
1/5Al
0.01O
2(PO
4)
0.0054, for Powdered.
Its preparation method:
(1) take Ni
3/5Co
1/5Mn
1/5(OH)
2The nickel Co-Mn compound of expression (the average grain diameter D50=13.5 μ m that adopts laser particle analyzer to survey, tap density 2.25g/cm
3, powder particle shape class is spherical) and 280.00g and lithium carbonate 125.07g and aluminium oxide 1.54g, dry type is mixed, is placed in Muffle furnace, then at 750 ℃ of sintering 20h, cooling rear fragmentation, screening, obtaining chemical formula is Li
1.12Ni
3/5Co
1/5Mn
1/5Al
0.01O
2The compd A of expression;
(2) adopt acid-base titration to record this Li
1.12Ni
3/5Co
1/5Mn
1/5Al
0.01O
2The remaining elemental lithium content of material is 1221ppm, the above-mentioned synthetic Li of weighing 200g
1.12Ni
3/5Co
1/5Mn
1/5Al
0.01O
2Material, add the lithium dihydrogen phosphate of 1.12g, and dry mixed, be placed in Muffle furnace, 800 ℃ of insulation 3h, cooling with stove after, crush and screen, obtain nickle cobalt lithium manganate Li
1.12Ni
3/5Co
1/5Mn
1/5Al
0.01O
2(PO
4)
0.0054.
Gained nickle cobalt lithium manganate Li
1.12Ni
3/5Co
1/5Mn
1/5Al
0.01O
2(PO
4)
0.0054Tap density is 2.65g/cm
3(adopting the GB/T5162-1985 method to test).
Embodiment 4
The multielement composite cathode material for lithium secondary battery of the present embodiment, its chemical formula are Li
1.04Ni
4/5Co
1/10Mn
1/10Zr
0.01O
2(PO
4)
0.01, for Powdered;
Its preparation method:
(1) take Ni
4/5Co
1/10Mn
1/10(OH)
2The nickel Co-Mn compound of expression (the average grain diameter D50=10.0 μ m that adopts laser particle analyzer to survey, tap density 2.0g/cm
3, powder particle shape class is spherical) and 280.00g and Lithium hydroxide monohydrate (purity 95%) 138.13g and zirconia 3.70g, dry type is mixed, is placed in Muffle furnace, then at 750 ℃ of sintering 20h, cooling rear fragmentation, screening, obtaining chemical formula is Li
1.04Ni
4/5Co
1/10Mn
1/10Zr
0.01O
2The compd A of expression;
(2) adopt acid-base titration to record this Li
1.04Ni
4/5Co
1/10Mn
1/10Zr
0.01O
2The remaining elemental lithium content of material is 2350ppm, the above-mentioned synthetic Li of weighing 200g
1.04Ni
4/5Co
1/10Mn
1/10Zr
0.01O
2Material, add the diammonium hydrogen phosphate of 2.68g, and dry mixed, be placed in Muffle furnace, 600 ℃ of insulation 3h, cooling with stove after, crush and screen, obtain nickle cobalt lithium manganate Li
1.04Ni
4/5Co
1/10Mn
1/10Zr
0.01O
2(PO
4)
0.01.
Gained nickle cobalt lithium manganate Li
1.04Ni
4/5Co
1/10Mn
1/10Zr
0.01O
2(PO
4)
0.01Tap density is 2.45g/cm
3(adopting the GB/T5162-1985 method to test).
Embodiment 5
The multielement composite cathode material for lithium secondary battery of the present embodiment, its chemical formula are Li
1.06Ni
4/5Co
1/5Ba
0.001O
2(PO
4)
0.015, for Powdered;
Its preparation method:
(1) take Ni
4/5Co
1/5(OH)
2The nickel cobalt compound of expression (the average grain diameter D50=10.2 μ m that adopts laser particle analyzer to survey, tap density 1.96g/cm
3, powder particle shape class is spherical) and 280.00g and Lithium hydroxide monohydrate (purity 95%) 139.45g and barium hydroxide 0.51g, dry type is mixed, is placed in Muffle furnace, then at 750 ℃ of sintering 20h, cooling rear fragmentation, screening, obtaining chemical formula is Li
1.06Ni
4/5Co
1/5Ba
0.001O
2The compd A of expression;
(2) adopt acid-base titration to record this Li
1.06Ni
4/5Co
1/5Ba
0.001O
2The remaining elemental lithium content of material is 3520ppm, the above-mentioned synthetic Li of weighing 200g
1.06Ni
4/5Co
1/5Ba
0.001O
2Material, add the ammonium dihydrogen phosphate of 3.51g, and dry mixed, be placed in Muffle furnace, 800 ℃ of insulation 3h, cooling with stove after, crush and screen, obtain nickle cobalt lithium manganate Li
1.06Ni
4/5Co
1/5Ba
0.001O
2(PO
4)
0.015.
Embodiment 6
The multielement composite cathode material for lithium secondary battery of the present embodiment, its chemical formula are Li
1.06Ni
1/2Co
1/5Mn
3/10Sr
0.007O
2(PO
4)
0.0030, for Powdered;
Its preparation method:
(1) take Ni
1/2Co
1/5Mn
3/10(OH)
2The nickel Co-Mn compound of expression (the average grain diameter D50=10.0 μ m that adopts laser particle analyzer to survey, tap density 2.01g/cm
3, powder particle shape class is spherical) and 280.00g and lithium carbonate 119.12g and strontium hydroxide 2.59g, dry type is mixed, is placed in Muffle furnace, then at 850 ℃ of sintering 20h, cooling rear fragmentation, screening, obtaining chemical formula is Li
1.06Ni
1/2Co
1/5Mn
3/10Sr
0.007O
2The compd A of expression;
(2) adopt acid-base titration to record this Li
1.06Ni
1/2Co
1/5Mn
3/10Sr
0.007O
2The remaining elemental lithium content of material is 658ppm, the above-mentioned synthetic Li of weighing 200g
1.06Ni
1/2Co
1/5Mn
3/10Sr
0.007O
2Material, add the ammonium dihydrogen phosphate of 0.70g, and dry mixed, be placed in Muffle furnace, 800 ℃ of insulation 3h, cooling with stove after, crush and screen, obtain nickle cobalt lithium manganate Li
1.06Ni
1/2Co
1/5Mn
3/10Sr
0.007O
2(PO
4)
0.0030.
Embodiment 7
The multielement composite cathode material for lithium secondary battery of the present embodiment, its chemical formula are Li
1.04Ni
4/5Co
1/5B
0.02O
2(PO
4)
0.012, for Powdered;
Its preparation method:
(1) take Ni
4/5Co
1/5(OH)
2The nickel cobalt compound of expression (the average grain diameter D50=10.1 μ m that adopts laser particle analyzer to survey, tap density 2.00g/cm
3, powder particle shape class is spherical) and 280.00g and Lithium hydroxide monohydrate (purity 95%) 136.82g and boric acid 3.68g, dry type is mixed, is placed in Muffle furnace, then at 800 ℃ of sintering 10h, cooling rear fragmentation, screening, obtaining chemical formula is Li
1.04Ni
4/5Co
1/5B
0.02O
2The compd A of expression;
(2) adopt acid-base titration to record this Li
1.04Ni
4/5Co
1/5B
0.02O
2The remaining elemental lithium content of material is 2850ppm, the above-mentioned synthetic Li of weighing 200g
1.04Ni
4/5Co
1/5B
0.02O
2Material, add the ammonium dihydrogen phosphate of 2.81g, and dry mixed, be placed in Muffle furnace, 700 ℃ of insulation 6h, cooling with stove after, crush and screen, obtain nickle cobalt lithium manganate Li
1.04Ni
4/5Co
1/5B
0.02O
2(PO
4)
0.012.
Comparative Examples 1
The secondary lithium batteries composite positive pole of this Comparative Examples, its chemical formula are Li
1.04Ni
1/2Co
1/5Mn
3/10Zr
0.01O
2.
Its preparation method:
Take Ni
1/2Co
1/5Mn
3/10(OH)
2The nickel Co-Mn compound of expression (the average grain diameter D50=5.3 μ m that adopts laser particle analyzer to survey, tap density 1.23g/cm
3, powder particle shape class is spherical) and 280.00g and lithium carbonate 116.89g and zirconia 3.74g, dry type is mixed, is placed in Muffle furnace, then at 850 ℃ of sintering 20h, cooling rear fragmentation, screening, obtain Li
1.04Ni
1/2Co
1/5Mn
3/10Zr
0.01O
2
Comparative Examples 2
The secondary lithium batteries composite positive pole of this Comparative Examples, its chemical formula are Li
1.04Ni
1/2Co
1/5Mn
3/10O
2.
Its preparation method:
Take Ni
1/2Co
1/5Mn
3/10(OH)
2The nickel Co-Mn compound of expression (the average grain diameter D50=5.3 μ m that adopts laser particle analyzer to survey, tap density 1.23g/cm
3, powder particle shape class is spherical) and 280.00g and lithium carbonate 116.89g, dry type is mixed, is placed in Muffle furnace, then at 850 ℃ of sintering 20h, cooling rear fragmentation, screening, obtain Li
1.04Ni
1/2Co
1/5Mn
3/10O
2.
Comparative Examples 3
The secondary lithium batteries composite positive pole of this Comparative Examples, its chemical formula are Li
1.12Ni
3/5Co
1/5Mn
1/5Al
0.01O
2(PO
4)
0.03.
Its preparation method:
(1) weighing 280.00g nickel cobalt manganese hydroxide (molecular formula Ni
3/5Co
1/5Mn
1/5(OH)
2, the average grain diameter D50=13.5 μ m that adopts laser particle analyzer to survey, tap density 2.25g/cm
3, powder particle shape class is spherical), lithium carbonate and the 1.54g aluminium oxide of 125.07g, dry type is mixed, be placed in Muffle furnace, 750 ℃ of sintering 20h, cooling with stove after, crush and screen, obtain Li
1.12Ni
3/5Co
1/5Mn
1/5Al
0.01O
2
(2) this Li that adopts acid-base titration to survey
1.12Ni
3/5Co
1/5Mn
1/5Al
0.01O
2The remaining elemental lithium content of material is 1221ppm, the above-mentioned synthetic Li of weighing 200g
1.12Ni
3/5Co
1/5Mn
1/5Al
0.01O
2Material, add the lithium dihydrogen phosphate of 6.36g, and dry mixed, be placed in Muffle furnace, 800 ℃ of insulation 3h, cooling with stove after, crush and screen, obtain the nickle cobalt lithium manganate Li that we need
1.12Ni
3/5Co
1/5Mn
1/5Al
0.01O
2(PO
4)
0.03.
Gained nickle cobalt lithium manganate Li
1.12Ni
3/5Co
1/5Mn
1/5Al
0.01O
2(PO
4)
0.03Tap density is 2.55g/cm
3(adopting the GB/T5162-1985 method to test tap density).
[battery making]
By embodiment 1-3 and Comparative Examples 1-3 gained nickle cobalt lithium manganate, PVDF (Kynoar), acetylene black and NMP (1-METHYLPYRROLIDONE) the ratio mixing of 100:2.3:2.3:45 in mass ratio, the slurry that solid content is 60-70% is made in stirring, slurry is coated on the aluminium foil that 16 μ m are thick, oven dry under 150 ℃, be cut into the sheet of 40 * 100mm, positive plate is made in roll-in under 7MPa pressure; By the ratio mixing of 100:1:1.7:2:130 in mass ratio of graphite, acetylene black, CMC (sodium carboxymethylcellulose), SBR (butadiene-styrene rubber breast) and water, the slurry that solid content is 40-50% is made in stirring, slurry is coated on the Copper Foil that 10 μ m are thick, oven dry under 120 ℃, be cut into the sheet of 42 * 102mm, negative plate is made in roll-in under 3MPa pressure; Barrier film is the polypropylene microporous barrier (Celgard 2400) of import; Electrolyte is 1mol/L LiPF6/ ethylene carbonate (EC)+dimethyl carbonate (DMC) (volume ratio 1:1), in glove box, is assembled into the lamination soft-package battery of 4 group of one cover.
[test of initial discharge capacity]
Under 25 ℃ of room temperatures, first adopt the 0.1C constant current charge to 4.2V on the battery of making, then with the constant voltage charge of 4.2V, cut-off current is 0.01C; Adopt the 0.1C constant-current discharge, cut-ff voltage is 2.75V, using the discharge capacity of this moment as initial discharge capacity.
[cycle performance test]
Under 25 ℃ of room temperatures, to 4.2V, then with the constant voltage charge of 4.2V, cut-off current is 0.01C with the constant current charge of 1C; With the 1C constant current discharge, cut-ff voltage 2.75V, in 100 weeks of circulation, obtain the circulation volume conservation rate with the discharge capacity in the 100th week than the discharge capacity in the 1st week.
[high-temperature storage performance test]
Under 25 ℃ of room temperatures, to 4.2V, then with the constant voltage charge of 4.2V, cut-off current is 0.01C with the constant current charge of 1C.Thereafter, with the 1C constant current discharge, cut-ff voltage 2.75V, using the discharge capacity of this moment capacity before preserving, then the volume before preserving with the drainage test.Then, again with the constant current charge of 1C to 4.2V, then, with the constant voltage charge of 4.2V, after cut-off current is 0.01C, at 85 ℃, preserve 24h.Finally, 25 ℃ with the 1C constant current discharge to 2.75V, using the capacity of the discharge capacity of this moment after preserving, and adopt simultaneously the volume after the drainage test is preserved.Therefore, based on following formula, calculate high-temperature charging guarantor property.
Capacity survival rate (%)=(capacity before capacity after preserving/preservation) * 100
Active material factor of created gas (cc/g)=(volume after preserving/preservation front volume-1)/active material weight
The test result of embodiment 1-3 and Comparative Examples 1-3 is listed in table 1.
The battery performance test result of table 1 embodiment 1-7 and Comparative Examples 1-3
As shown in Table 1, only by the trace doped circulation that can only improve product, but not obvious to the aerogenesis control of product, then in conjunction with phosphatic surface treatment, the gas production of product has obtained inhibition.
Electrical property result by embodiment 3 in contrast table 1 and Comparative Examples 3 can be found out, when the phosphate treatment amount is too much, easily cause the decline of product capacity and circulation volume conservation rate, illustrate that the mol ratio of the Li/P of product remnants should be controlled in suitable scope.
Claims (6)
1. the preparation method of a multielement composite cathode material for lithium secondary battery, is characterized in that, comprises the following steps:
(1) take Ni
xCo
yMn
1-x-y(OH)
2Compound, lithium salts or lithia or the lithium hydroxide of expression, contain the compound of element M, making the Li:Ni:Co:Mn:M stoichiometric proportion is a:x:y:(1-x-y): z, wherein a, x, y, z are respectively 0.8≤a≤1.2,0<x<1,0<y<1, x+y≤1,0.0005≤z≤0.02, mix, then at 700-950 ℃ of sintering 6-24h, cooling rear fragmentation, screening, obtaining chemical formula is Li
aNi
xCo
yMn
1-x-yM
zO
2The compd A of expression;
(2) the remaining elemental lithium content of testing procedure (1) gained compd A, add the phosphorus-containing compound of Li/P molar ratio>=3, then at 300-900 ℃ of heat treatment 2-10h, cooling after, fragmentation, screening, namely obtaining chemical formula is Li
aNi
xCo
yMn
1-x-yM
zO
2(PO
4)
bThe multielement composite cathode material for lithium secondary battery of expression, for Powdered; Described powder is the Conglobation type particle; In described chemical formula, M is one or two or more kinds the element that is selected from Mg, Al, Zr, Ba, Sr, B, and a, x, y, z and b are the values of the mol ratio of coherent element, be respectively 0.8≤a≤1.2,0<x<1,0<y<1, x+y≤1,0.0005≤z≤0.02,0<b≤0.02;
Tap density>=the 1.5g/cm of described multielement composite cathode material for lithium secondary battery
3.
2. the preparation method of multielement composite cathode material for lithium secondary battery according to claim 1, is characterized in that, comprises the following steps:
(1) take Ni
xCo
yMn
1-x-y(OH)
2Compound, lithium salts or lithia or the lithium hydroxide of expression, contain the compound of element M, making the Li:Ni:Co:Mn:M stoichiometric proportion is a:x:y:(1-x-y): z, wherein a, x, y, z are respectively 0.8≤a≤1.2,0<x<1,0<y<1, x+y≤1,0.0005≤z≤0.02, mix, then at 750 ℃ of sintering 20h, cooling rear fragmentation, screening, obtaining chemical formula is Li
aNi
xCo
yMn
1-x-yM
zO
2The compd A of expression;
(2) the remaining elemental lithium content of testing procedure (1) gained compd A, add the phosphorus-containing compound of Li/P molar ratio>=3,800 ℃ of heat treatment 3h then, and cooling rear fragmentation, screening, obtaining chemical formula is Li
aNi
xCo
yMn
1-x-yM
zO
2(PO
4)
bThe multielement composite cathode material for lithium secondary battery of expression.
3. the preparation method of multielement composite cathode material for lithium secondary battery according to claim 1 and 2, is characterized in that, described Ni
xCo
yMn
1-x-y(OH)
2Compound tap density>=the 1.0g/cm of expression
3, the average grain diameter of laser diffractometry test is 5-20 μ m, powder particle be shaped as near-spherical.
4. the preparation method of multielement composite cathode material for lithium secondary battery according to claim 1 and 2, is characterized in that, described phosphorus-containing compound is at least a in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, lithium dihydrogen phosphate.
5. the preparation method of multielement composite cathode material for lithium secondary battery according to claim 1 and 2, is characterized in that, the described compound that contains element M is salt, oxide, hydroxide or the inorganic acid that contains element M.
6. the preparation method of multielement composite cathode material for lithium secondary battery according to claim 1 and 2, is characterized in that, described lithium salts is lithium carbonate.
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| CN103413932B (en) * | 2013-08-19 | 2015-07-29 | 北大先行科技产业有限公司 | A kind of modification single crystal type multielement anode material and preparation method thereof |
| CN105591096A (en) * | 2016-03-03 | 2016-05-18 | 无锡凯力克能源材料有限公司 | Industrial production method of nickel cobalt lithium manganite ternary positive electrode material with cycle life more than 3000 times |
| JP7191489B2 (en) * | 2017-07-14 | 2022-12-19 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for producing electrode active material |
| CN108011100A (en) * | 2017-12-15 | 2018-05-08 | 中国科学院成都有机化学有限公司 | A kind of tertiary cathode material of surface reaction cladding and preparation method thereof |
| CN109686968A (en) * | 2018-12-12 | 2019-04-26 | 无锡晶石新型能源股份有限公司 | The preparation method of high voltage nickel cobalt-manganese ternary material |
| CN109860509B (en) * | 2019-01-14 | 2021-02-26 | 中国电力科学研究院有限公司 | Preparation method of anion co-doped lithium-rich manganese-based solid solution cathode material |
| CN110911686A (en) * | 2019-12-06 | 2020-03-24 | 江西理工大学 | Method for inhibiting voltage attenuation of lithium-rich manganese-based positive electrode material in charge-discharge cycle process |
| CN114408986B (en) * | 2022-01-21 | 2024-02-13 | 陕西彩虹新材料有限公司 | Nanoscale monocrystal ternary cathode material and preparation method thereof |
| CN114725357B (en) * | 2022-05-06 | 2024-02-20 | 蜂巢能源科技股份有限公司 | Method for reducing residual sodium content of sodium ion positive electrode material |
| CN114883555B (en) * | 2022-06-09 | 2024-01-30 | 贵州高点科技有限公司 | Multiphase manganese material, preparation method thereof, positive plate and secondary battery |
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