CN107611402A - Compound lithium-rich positive electrode and preparation method thereof - Google Patents
Compound lithium-rich positive electrode and preparation method thereof Download PDFInfo
- Publication number
- CN107611402A CN107611402A CN201710822455.5A CN201710822455A CN107611402A CN 107611402 A CN107611402 A CN 107611402A CN 201710822455 A CN201710822455 A CN 201710822455A CN 107611402 A CN107611402 A CN 107611402A
- Authority
- CN
- China
- Prior art keywords
- sources
- lithium
- positive electrode
- rich
- ybaco
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 97
- 150000001875 compounds Chemical class 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 110
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 30
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 239000011358 absorbing material Substances 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract 2
- 238000000576 coating method Methods 0.000 claims abstract 2
- 238000000975 co-precipitation Methods 0.000 claims description 23
- 239000010405 anode material Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- 238000000227 grinding Methods 0.000 claims description 11
- 238000005253 cladding Methods 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 235000019628 coolness Nutrition 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 abstract description 17
- 239000001301 oxygen Substances 0.000 abstract description 17
- 238000001994 activation Methods 0.000 abstract description 4
- 239000011572 manganese Substances 0.000 description 70
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 67
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229940011182 cobalt acetate Drugs 0.000 description 3
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 229940078494 nickel acetate Drugs 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910010372 Li1.28Ni0.08Mn0.64O2 Inorganic materials 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 2
- 229910001626 barium chloride Inorganic materials 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 235000013495 cobalt Nutrition 0.000 description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229940093474 manganese carbonate Drugs 0.000 description 2
- 239000011656 manganese carbonate Substances 0.000 description 2
- 235000006748 manganese carbonate Nutrition 0.000 description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 2
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DEXZEPDUSNRVTN-UHFFFAOYSA-K yttrium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Y+3] DEXZEPDUSNRVTN-UHFFFAOYSA-K 0.000 description 2
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- 229910016104 LiNi1 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- DUSUCKWNBGMKRV-UHFFFAOYSA-N acetic acid;yttrium Chemical compound [Y].CC(O)=O DUSUCKWNBGMKRV-UHFFFAOYSA-N 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
- 239000005030 aluminium foil Substances 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 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
- 229940008015 lithium carbonate Drugs 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000447 polyanionic polymer Polymers 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
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 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 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to a kind of compound lithium-rich positive electrode and preparation method thereof.The material is by oxygen-absorbing material YBaCo4O7With lithium-rich positive electrode Li [Li1/3‑2x/3Nix‑aCo2aMn2/3‑x/3‑a]O2Adulterating or coating or the compound lithium-rich positive electrode directly is made by way of physical mixed, its expression formula is：(1‑m)Li[Li1/3‑2x/3Nix‑aCo2aMn2/3‑x/3‑a]O2•mYBaCo4O7, wherein, 0≤a≤x, 0<x<0.5,0.1%≤m（YBaCo4O7The amount fraction of material in the composite）≤1%.YBaCo4O7Material can effectively absorb lithium-rich positive electrode Li [Li under high potential1/3‑2x/3Nix‑aCo2aMn2/3‑x/3‑a]O2The active oxygen generation YBaCo discharged in initial charge activation process4O7+δ（δ is oxygen absorbed）, thus it is remarkably improved the security performance of the lithium-ion battery system using lithium-rich positive electrode.
Description
Technical field
The present invention relates to electrode material, is a kind of compound lithium-rich positive electrode and preparation method thereof specifically.
Background technology
Compared to other secondary cells, lithium ion battery have energy density is high, have extended cycle life, memory-less effect,
The advantages that green, it is widely used to electric automobile and portable type electronic product.The energy density of lithium ion battery is shadow
Electric automobile during traveling mileage, the main factor of portable type electronic product working time are rung, thus improves lithium ion cell positive
The energy density of material is always the emphasis of researcher's work.Current commercialized positive electrode has LiCoO2、LiNi1/3Co1/ 3Mn1/3O2And LiFePO4Deng the actual discharge specific capacity of these positive electrodes is between 140-170 mAhg-1Between.And rich lithium layer
Shape positive electrode Li [Li1/3-2x/3Nix-aCo2aMn2/3-x/3-a]O2, (0≤a≤x,0<x<0.5, the expression formula can also be written as
Lower form：yLi2MnO3•(1-y)LiNi1/2-bCo2bMn1/2-bO2) because with more than 250 mAh g-1Height ratio capacity, thus
As study hotspot in recent years.In addition, lithium-rich positive electrode also has the advantages that cost is low, small toxicity.Filled first
In electric process, the class Li in lithium-rich material2MnO3Structure can activate, and deviate from Li+And active oxygen atom, generate stratiform
LiMnO2Continue to participate in Li+Embedded abjection reaction, therefore, lithium-rich material has higher charging and discharging capacity（J.
Am. Chem. Soc. 2006, 128, 8694-8698）.However, this electrochemical reaction mechanism there is also it is larger the shortcomings that,
The oxygen atom of generation has very high electro-chemical activity, and oxidisability is very strong, and the electrolyte in lithium ion battery is organic matter, is
Inflammable constituent, under the conditions of existing for active oxygen, there is the potential safety hazards such as on fire or even blast in lithium ion battery.J. Mater.
Chem. A, 2014,2,7454-7460 and J. Electrochem. Soc. 2015,162, A1899-A1904 distinguish
Report and the method that oxygen separates out in lithium-rich material is suppressed using polyanion doping to a certain extent；Adv. Funct.
Mater. 2014,24,5112-5118 is reported using B（Boron）Doping suppresses oxygen in rich lithium layer material and analysed to a certain extent
The method gone out.But using modified methods such as doping, suppress the precipitation of active oxygen in lithium-rich positive electrode, then Fu Li
Layered oxide positive electrode cannot be activated fully, it is impossible to give play to the high power capacity of lithium-rich positive electrode completely.
That is, the security performance and chemical property of lithium-rich material are conflicting to a certain extent, it is difficult to make the best of both worlds.
The content of the invention
The present invention provides compound lithium-rich positive electrode and preparation method thereof, at least up to reduces lithium-rich positive pole material
Expect the analysis oxygen amount in initial charge activation process, improve the purpose of the security performance of lithium-rich oxide anode material.
To solve above technical problem, according to an aspect of the present invention, there is provided a kind of compound lithium-rich positive electrode
Preparation method, oxygen-absorbing material YBaCo4O7With lithium-rich positive electrode Li [Li1/3-2x/3Nix-aCo2aMn2/3-x/3-a]O2Pass through
Doping or the mode of cladding or directly physical mixed are combined the compound lithium-rich positive electrode, and its expression formula is：
(1-m)Li[Li1/3-2x/3Nix-aCo2aMn2/3-x/3-a]O2•mYBaCo4O7, wherein, 0≤a≤x, 0<x<0.5,0.1%≤m
（YBaCo4O7The amount fraction of material in the composite）≤1%.
Further, for doped and compounded mode, by Li sources, Ni sources, the direct physical mixed in Co sources and Mn sources, or by Ni
The product that source, Co sources and Mn sources handle to obtain using coprecipitation mixes with Li sources, obtains persursor material 1；By Y sources, Ba sources
With the direct physical mixed in Co sources, or by Y sources, Ba sources and Co sources using coprecipitation handle, obtain persursor material 2；By forerunner
Body material 1 and persursor material 2 in proportion mixed grinding, mixing, be calcined 5-30 hours at 800-1200 DEG C after obtain YBaCo4O7
The lithium-rich positive electrode of doping.
Preferably, the persursor material 1 and persursor material 2 mixed grinding after 500 DEG C of pre-burning 4h are cooled down respectively.
Further, for covered composite yarn mode, by Y sources, Ba sources, Co sources and lithium-rich oxide anode material point
Dissipate and obtain suspension in water or ethanol, the persursor material that the suspension obtains after being evaporated roasts in the range of 800-1200 DEG C
Burning 5-30 hours obtain YBaCo4O7The lithium-rich positive electrode of cladding.
Preferably, by Li sources, Ni sources, the direct physical mixed in Co sources and Mn sources, or by Ni sources, Co sources and Mn sources using altogether
The product that the precipitation method handle to obtain mixes with Li sources, obtains persursor material 1, and the persursor material 1 is in 800-1200 DEG C of scope
Interior roasting 5-30 hours, obtain described lithium-rich oxide anode material Li [Li1/3-2x/3Nix-aCo2aMn2/3-x/3-a]O2
Preferably, the persursor material 1 is ground after 500 DEG C of pre-burning 4h are cooled down, then it is calcined into 5-30 at 800-1200 DEG C
Hour, obtain the lithium-rich oxide anode material.
Further, for direct physical mixed, by Li sources, Ni sources, the direct physical mixed in Co sources and Mn sources, or by Ni
The product that source, Co sources and Mn sources handle to obtain using coprecipitation mixes with Li sources, obtains persursor material 1, the presoma material
Material 1 is calcined 5-30 hours in the range of 800-1200 DEG C, obtains described lithium-rich oxide anode material Li [Li1/3-2x/ 3Nix-aCo2aMn2/3-x/3-a]O2；By Y sources, the direct physical mixed in Ba sources and Co sources, or by Y sources, Ba sources and Co sources using co-precipitation
Method processing, obtain persursor material 2, the persursor material 2 carried out in the range of 800-1200 DEG C be calcined 5-30 hours can obtain
To prepared YBaCo4O7Material；By lithium-rich oxide anode material Li [Li1/3-2x/3Nix-aCo2aMn2/3-x/3-a]O2With
YBaCo4O7Material directly mixes, and obtains the compound lithium-rich positive electrode.
According to another aspect of the present invention, there is provided a kind of compound lithium-rich positive pole being prepared by method made above
Material.
According to another aspect of the present invention, there is provided one kind has lithium-ion electric made of above-mentioned compound lithium-rich positive electrode
Pond.
The present invention is by YBaCo4O7The method that material passes through physical mixed, doping or cladding with lithium-rich positive electrode
After preparing composite, YBaCo4O7Material can effectively absorb lithium-rich positive electrode Li [Li under high potential1/3-2x/ 3Nix-aCo2aMn2/3-x/3-a]O2The active oxygen generation YBaCo discharged in initial charge activation process4O7+δ（δ is oxygen absorbed）, because
And it is remarkably improved the security performance of the lithium-ion battery system using lithium-rich positive electrode.
Brief description of the drawings
Fig. 1 is the pressure comparison test result of two kinds of lithium ion batteries in comparative example 1.
Fig. 2 is the pressure comparison test result of two kinds of lithium ion batteries in comparative example 2.
Fig. 3 is the pressure comparison test result of two kinds of lithium ion batteries in comparative example 3.
Fig. 4 is the pressure comparison test result of two kinds of lithium ion batteries in comparative example 4.
Fig. 5 is the pressure comparison test result of two kinds of lithium ion batteries in comparative example 5.
Fig. 6 is the pressure comparison test result of two kinds of lithium ion batteries in comparative example 6.
Embodiment
A kind of typical embodiment of the present invention, there is provided a kind of compound lithium-rich positive electrode preparation method, by
Oxygen-absorbing material YBaCo4O7With lithium-rich positive electrode Li [Li1/3-2x/3Nix-aCo2aMn2/3-x/3-a]O2By adulterating or wrapping
Cover or the compound lithium-rich positive electrode is made in the mode of directly physical mixed, its expression formula is：(1-m)Li
[Li1/3-2x/3Nix-aCo2aMn2/3-x/3-a]O2•mYBaCo4O7, wherein, 0≤a≤x, 0<x<0.5,0.1%≤m（YBaCo4O7Multiple
The amount fraction of material in condensation material）≤1%.Layered oxide material YBaCo4O7（Space group P63mc)）, there is oxygen adsorptivity
Can, all have broad application prospects in fields such as lambda sensor, storage oxygen.This kind of material behind Y positions and Co positions doping vario-property
Also there is good performance in terms of oxygen uptake.By YBaCo4O7Material and lithium-rich positive electrode by physical mixed, doping or
After the method for person's cladding prepares composite, YBaCo4O7Material can effectively absorb lithium-rich positive electrode under high potential
Li[Li1/3-2x/3Nix-aCo2aMn2/3-x/3-a]O2The active oxygen generation YBaCo discharged in initial charge activation process4O7+δ（δ is
Oxygen absorbed）, thus it is remarkably improved the security performance of the lithium-ion battery system using lithium-rich positive electrode.
In a kind of relative specific embodiment, there is provided compound lithium-rich positive pole material is made by way of doping
The method of material.Li sources, Ni sources, the direct physical mixed in Co sources and Mn sources are obtained into persursor material 1, or by Ni sources, Co sources and
The product that Mn sources handle to obtain using coprecipitation mixes with Li sources, obtains persursor material 1；Y sources, Ba sources and Co sources is direct
Physical mixed obtains persursor material 2, or Y sources, Ba sources and Co sources are handled using coprecipitation, obtains persursor material 2；Will
Persursor material 1 and persursor material 2 in proportion mixed grinding, mixing, be calcined 5-30 hours at 800-1200 DEG C after obtain
YBaCo4O7The lithium-rich positive electrode of doping.
In a preferred embodiment, the persursor material 1 and persursor material 2 cool down in 500 DEG C of pre-burning 4h respectively
Mixed grinding afterwards.
In another relative specific embodiment, there is provided compound lithium-rich positive pole is made by way of cladding
The method of material.Y sources, Ba sources, Co sources and lithium-rich oxide anode material are scattered in water or ethanol obtain it is suspended
Liquid, the persursor material that the suspension obtains after being evaporated are calcined 5-30 hours in the range of 800-1200 DEG C and obtain YBaCo4O7Bag
The lithium-rich positive electrode covered.
In a preferred embodiment, by Li sources, Ni sources, the direct physical mixed in Co sources and Mn sources, or by Ni sources, Co sources
The product for handling to obtain using coprecipitation with Mn sources mixes with Li sources, obtains persursor material 1, the persursor material 1 exists
5-30 hours are calcined in the range of 800-1200 DEG C, obtain described lithium-rich oxide anode material Li [Li1/3-2x/3Nix- aCo2aMn2/3-x/3-a]O2
In a preferred embodiment, the persursor material 1 is ground after 500 DEG C of pre-burning 4h are cooled down, then by it in 800-
1200 DEG C of roasting 5-30 hours, obtain the lithium-rich oxide anode material.
In another relative specific embodiment, there is provided compound rich lithium is made by way of direct physical mixed
The method of layered cathode material.Adopted by Li sources, Ni sources, the direct physical mixed in Co sources and Mn sources, or by Ni sources, Co sources and Mn sources
Mixed with the product that coprecipitation handles to obtain with Li sources, obtain persursor material 1, the persursor material 1 is at 800-1200 DEG C
In the range of be calcined 5-30 hours, obtain described lithium-rich oxide anode material Li [Li1/3-2x/3Nix- aCo2aMn2/3-x/3-a]O2；By Y sources, the direct physical mixed in Ba sources and Co sources, or by Y sources, Ba sources and Co sources using at coprecipitation
Reason, obtain persursor material 2, the persursor material 2 carried out in the range of 800-1200 DEG C be calcined 5-30 hours can obtain institute
The YBaCo of preparation4O7Material；By lithium-rich oxide anode material Li [Li1/3-2x/3Nix-aCo2aMn2/3-x/3-a]O2With
YBaCo4O7Material directly mixes, and obtains the compound lithium-rich positive electrode.
In embodiment of above, it is preferable that Ni sources are selected from nickel acetate, nickel oxalate, nickel nitrate, nickelous carbonate, hickelous nydroxide
At least one of；Co salt in cobaltous sulfate, cobalt acetate, cobalt oxalate, cobalt nitrate, carbonate and hydroxide cobalt at least one
Kind；Mn salt is selected from least one of manganese acetate, manganese oxalate, manganese nitrate, carbonate and hydroxide manganese.
Preferably, Y sources are selected from yttria, yttrium carbonate, in yttrium nitrate, yttrium hydroxide, acetic acid yttrium, yttrium chloride at least
It is a kind of；Ba sources are selected from least one of barium carbonate, barium nitrate, barium hydroxide, barium acetate, barium chloride；Co salt is selected from three oxidations
At least one of two cobalts, cobaltosic oxide, hydroxide cobalt, cobalt acetate, cobalt nitrate and cobalt chloride.
A kind of another typical embodiment of the invention, there is provided compound rich lithium layer being prepared by method made above
Shape positive electrode.Compound lithium-rich positive electrode expression formula is：(1-m)Li[Li1/3-2x/3Nix-aCo2aMn2/3-x/3-a]O2•
mYBaCo4O7, wherein, 0≤a≤x, 0<x<0.5,0.1%≤m（YBaCo4O7The amount fraction of material in the composite）≤
1%.If m<0.1%, the oxygen of lithium-rich positive electrode release is not fully absorbed；If m>1%, YBaCo4O7As nonactive
Electrode material will significantly reduce the specific discharge capacity of composite positive pole.
In another typical embodiment of the invention, there is provided one kind has made of above-mentioned compound lithium-rich positive electrode
Lithium ion battery.
Further clear, complete explanation is made to technical solution of the present invention and technique effect with reference to some embodiments.
Embodiment 1
According to Li:Ni:Mn mol ratios are=1.2:0.2:Lithium carbonate, nickel acetate and manganese carbonate are well mixed by 0.6 ratio, and
It is placed in Muffle furnace and obtains persursor material 1 after 500 DEG C of pre-burning 4h.According to Y:Ba:Co mol ratios are 1:1:4 ratio will
Yttrium nitrate, barium carbonate and cobalt carbonate are well mixed, and are placed in Muffle furnace and are obtained persursor material 2 after 500 DEG C of pre-burning 4h.
By persursor material 1 and persursor material 2 according to Li:Ni:Mn:Y:Ba:Co=1.2:0.2:0.6:0.002:
0.002:0.008 ratio grinding, mix, and be placed on 900 DEG C of roasting 10h in Muffle furnace, you can obtain YBaCo4O7Doping
The compound lithium-rich positive electrode 0.998Li [Li of high safety0.2Ni0.2Mn0.6]O2•0.002YBaCo4O7。
Embodiment 2
According to Li:Ni:Co:Mn mol ratios are=1.11:0.3:0.06:0.53 ratio aoxidizes lithium hydroxide, nickel acetate, four
Three cobalts and manganese carbonate are well mixed, and obtain mixing material.The mixing material is placed in Muffle furnace after 500 DEG C of pre-burning 4h coolings and ground
Mill, 1200 DEG C of roasting 5h in Muffle furnace are placed on again, obtain lithium-rich oxide anode material
Li1.11Ni0.30Co0.06Mn0.53O2.According to mol ratio Li1.11Ni0.30Co0.06Mn0.53O2:Y:Ba:Co=1:0.001:0.001:
Above-mentioned lithium-rich oxide anode material, yttrium hydroxide, barium hydroxide and cobalt acetate are dispersed in water by 0.004 ratio,
Obtain suspension.Under continuous agitation, suspension is evaporated to obtain persursor material, persursor material is placed in Muffle
1200 degree of roasting 5h can obtain YBaCo in stove4O7The compound lithium-rich positive electrode of high safety of cladding
0.999Li1.11Ni0.30Co0.06Mn0.53O2•0.001YBaCo4O7。
Embodiment 3
By NiSO4And MnSO4The ratio that mol ratio according to Ni: Mn is 0.416: 0.528 mixes in deionized water, obtains
Mixed liquor；Under conditions of pH value is 10.2, the mixed solution of the mixed liquor and hydroxide and ammoniacal liquor is squeezed into altogether respectively
Coprecipitation reaction is carried out in precipitation reaction kettle, is dried after completion of the reaction, obtains persursor material [Ni0.441Mn0.559](OH)2.Will
Above-mentioned persursor material mixes with lithium salts according to Li: Ni: Mn mol ratio for 1.056: 0.416: 0.528,900 DEG C of roasting 6h,
Obtain described lithium-rich positive electrode Li [Li0.056Ni0.416Mn0.528]O2.By Y2O3、BaCO3With Co (CH3COO)2According to
Y:Ba:Co mol ratio is 1:1:4 ratio is well mixed, and is placed in Muffle furnace at 800 DEG C and is calcined 30h, after cooling, will be roasted
Material after burning grinds and obtains YBaCo4O7Material.Lithium-rich positive electrode Li1.056Ni0.416Mn0.528O2With oxygen-absorbing material
YBaCo4O7Material is according to mol ratio 99：1 directly mixes, and obtains the compound lithium-rich positive electrode of high safety
0.99Li1.11Ni0.30Co0.06Mn0.53O2•0.01YBaCo4O7。
Embodiment 4
By NiNO3、Co(SO4)2、Mn(CH3COO)2According to Ni:Co:Mn mol ratio is 0.15:0.1:0.55 ratio dissolving
In deionized water, mixed liquor is obtained；Under conditions of pH value is 9.9, by the mixing of the mixed liquor and sodium carbonate and ammoniacal liquor
Solution is squeezed into respectively carries out coprecipitation reaction in coprecipitation reaction kettle, dry after completion of the reaction, obtain persursor material
[Ni0.1875Co0.125Mn0.6875]CO3.By above-mentioned persursor material and lithium salts according to Li:Ni:Co:Mn mol ratio is 1.2:
0.15:0.1:0.55 mixes, and then cooling obtains powder body material A after 500 DEG C of pre-burning 4h.
By Y (NO3)3、BaCl2、Co(SO4)2According to Y：Ba: Co mol ratio is 1:1:4 ratio is dissolved in deionized water
In, obtain mixed liquor；Under conditions of pH value is 12, the mixed solution of the mixed liquor and hydroxide and ammoniacal liquor is beaten respectively
Enter and coprecipitation reaction is carried out in coprecipitation reaction kettle, dry after completion of the reaction, obtain persursor material [Y0.167Ba0.167Co0.666]
(OH)2.167.Then above-mentioned persursor material is cooled down after 500 DEG C of pre-burning 4h and obtains powder body material B.
By powder body material A and B according to Ni:Y mol ratios are 597:20 ratio mixed grinding, then under the conditions of 850 DEG C
Roasting 10h can obtain YBaCo4O7The compound lithium-rich positive electrode 0.995Li of high safety of doping
[Li0.2Ni0.15Co0.1Mn0.55]O2•0.005YBaCo4O7。
Embodiment 5
By NiNO3、Mn(CH3COO)2According to Ni:Mn mol ratios are 0.083:0.639 ratio is dissolved in deionized water, is obtained
Mixed liquor；Under conditions of pH value is 8.5, the mixed solution of the mixed liquor and sodium carbonate and ammoniacal liquor is squeezed into co-precipitation respectively
Coprecipitation reaction is carried out in reactor, is dried after completion of the reaction, obtains persursor material [Ni0.115Mn0.885]CO3.Before above-mentioned
Body material is driven with lithium salts according to Li:Ni:Mn mol ratio is 1.28: 0.083：0.639 mixes, then by it in 500 DEG C of pre-burning 4h
Afterwards, it is calcined 6h under the conditions of 900 DEG C after cooling grinding and can obtain lithium-rich material Li1.28Ni0.08Mn0.64O2。
By above-mentioned lithium-rich material and Y2O3, BaCO3And Co3O4According to Li1.28Ni0.08Mn0.64O2：Y：Ba：Co mol ratios
For 1:0.0081: 0.0081:0.0324 is scattered in ethanol, obtains suspension.Under continuous agitation, by suspension
It is evaporated to obtain persursor material, persursor material is placed in into 1200 degree of roasting 5h in Muffle furnace can obtain YBaCo4O7Cladding
The compound lithium-rich positive electrode 0.992Li [Li of high safety0.2Ni0.15Co0.1Mn0.55]O2•0.08YBaCo4O7。
Embodiment 6
By NiSO4、CoCl2With Mn (NO3)2According to Ni: Co：Mn mol ratio is 1:1:4 ratio mixes in deionized water,
Obtain mixed liquor；Under conditions of pH value is 11.5, the mixed solution of the mixed liquor and hydroxide and ammoniacal liquor is beaten respectively
Enter and coprecipitation reaction is carried out in coprecipitation reaction kettle, dry after completion of the reaction, obtain persursor material (Ni1/6Co1/6Mn4/6)
(OH)2.By above-mentioned persursor material and lithium salts according to Li: Ni: Co：Mn mol ratio is 1.2: 0.133：0.133: 0.534
Ratio mixes, and after 4h cooling grindings are calcined under the conditions of 500 DEG C, then is calcined 30h under the conditions of 800 DEG C, you can described in obtaining
Lithium-rich positive electrode Li [Li0.2Ni0.133Co0.133Mn0.534]O2。
By Y2O3、BaCO3With Co (CH3COO)2According to Y:Ba:Co mol ratio is 1:1:4 ratio is well mixed, and is placed in
After being calcined 4h cooling grindings in Muffle furnace under the conditions of 500 DEG C, then it is calcined 10h under the conditions of 1200 DEG C and obtains YBaCo4O7Material.
Lithium-rich positive electrode Li1.056Ni0.416Mn0.528O2With oxygen-absorbing material YBaCo4O7Material in molar ratio 99.9：0.1 is directly mixed
Close, obtain the compound lithium-rich positive electrode of high safety.0.999Li[Li0.2Ni0.133Co0.133Mn0.534]O2•
0.001YBaCo4O7
Embodiment 7
Compound lithium-rich positive electrode prepared by institute's any of the above embodiment, conductive black, Kynoar（PVDF）Press
According to mass ratio 8:1:1 adds in power mixer, adds appropriate 1-METHYLPYRROLIDONE, stirring a period of time to uniform state
Form homogenate, then will homogenate coated on aluminium foil, drying, vacuumize, then roll-in, be cut into positive plate；Using graphite as negative pole,
Microporous polypropylene membrane is barrier film, LiPF6Concentration is 1mol/L ethylene carbonate（EC）And dimethyl carbonate（DMC）（Volume ratio
For 1:1）Mixed solution be electrolyte, using metal aluminum hull as battery case, lithium ion battery is assembled into special drying room.
Material analyses the test of oxygen amount
The lithium-ion-power cell that positive electrode is assembled into, by the way that battery is connected with accurate differential manometer, initial charge arrives
After 4.9V, the pressure value of differential manometer is read（That is inside battery and outside pressure differential）.Pressure value is bigger, then illustrates the analysis of material
Oxygen amount is bigger.
Comparative example 1
The persursor material 1 of embodiment 1 is placed in 900 DEG C of roasting 10h in Muffle furnace and prepares conventional lithium-rich positive electrode
Li1.20Ni0.20Mn0.60O2, and it is assembled into No. 1 lithium ion battery.The YBaCo that embodiment 1 is prepared4O7The high safety of doping is answered
Close lithium-rich positive electrode 0.998Li [Li0.2Ni0.2Mn0.6]O2•0.002YBaCo4O7It is assembled into No. 2 lithium ion batteries.Enter
Row pressure comparison is tested, as a result as shown in Figure 1.
Comparative example 2
The conventional lithium-rich oxide anode material Li that embodiment 2 is obtained1.11Ni0.30Co0.06Mn0.53O2It is assembled into No. 3 lithiums
Ion battery.Embodiment 2 obtains YBaCo4O7The compound lithium-rich positive electrode of high safety of cladding
0.999Li1.11Ni0.30Co0.06Mn0.53O2•0.001YBaCo4O7It is assembled into No. 4 lithium ion batteries.Pressure comparison test is carried out,
As a result it is as shown in Figure 2.
Comparative example 3
The conventional lithium-rich oxide anode material Li that embodiment 3 is obtained1.056Ni0.416Mn0.528O2Be assembled into No. 5 lithiums from
Sub- battery.Embodiment 3 obtains the compound lithium-rich positive electrode 0.99Li of high safety1.11Ni0.30Co0.06Mn0.53O2•
0.01YBaCo4O7It is assembled into No. 6 lithium ion batteries.Pressure comparison test is carried out, as a result as shown in Figure 3.
Comparative example 4
The powder body material A that embodiment 4 obtains is calcined 10h under the conditions of 850 DEG C, the lithium-rich positive electrode Li that will be obtained
[Li0.2Ni0.15Co0.1Mn0.55]O2It is assembled into No. 7 lithium ion batteries.Embodiment 4 obtains YBaCo4O7The compound richness of high safety of doping
Lithium layered cathode material 0.995Li [Li0.2Ni0.15Co0.1Mn0.55]O2•0.005YBaCo4O7It is assembled into No. 8 lithium ion batteries.Enter
Row pressure comparison is tested, as a result as shown in Figure 4.
Comparative example 5
The conventional lithium-rich oxide anode material Li that embodiment 5 is obtained1.28Ni0.08Mn0.64O2It is assembled into No. 9 lithium ions
Battery.Embodiment 5 obtains YBaCo4O7The compound lithium-rich positive electrode 0.992Li of high safety of cladding
[Li0.2Ni0.15Co0.1Mn0.55]O2•0.08YBaCo4O7It is assembled into No. 10 lithium ion batteries.Pressure comparison test is carried out, as a result such as
Shown in Fig. 5.
Comparative example 6
The conventional lithium-rich oxide anode material Li [Li that embodiment 6 is obtained0.2Ni0.133Co0.133Mn0.534]O2It is assembled into
No. 11 lithium ion batteries.Embodiment 6 obtains the compound lithium-rich positive electrode 0.999Li of high safety
[Li0.2Ni0.133Co0.133Mn0.534]O2•0.001YBaCo4O7It is assembled into No. 12 lithium ion batteries.Carry out pressure comparison test, knot
Fruit is as shown in Figure 6.
The scope of protection of present invention is not limited to above embodiment, to those skilled in the art, this
Invention can have a various deformation and change, all designs in the present invention with made within principle any modification, improvement and be equal
Replacing should all be included within protection scope of the present invention.
Claims (9)
- A kind of 1. preparation method of compound lithium-rich positive electrode, it is characterised in that：Oxygen-absorbing material YBaCo4O7With lithium-rich Positive electrode Li [Li1/3-2x/3Nix-aCo2aMn2/3-x/3-a]O2Adulterating or coating or be directly made by way of physical mixed The compound lithium-rich positive electrode, its expression formula are：(1-m)Li[Li1/3-2x/3Nix-aCo2aMn2/3-x/3-a]O2• mYBaCo4O7, wherein, 0≤a≤x, 0<x<0.5,0.1%≤m（YBaCo4O7The amount fraction of material in the composite）≤ 1%。
- 2. according to the method for claim 1, it is characterised in that：By Li sources, Ni sources, the direct physical mixed in Co sources and Mn sources, Or the product for handling to obtain using coprecipitation by Ni sources, Co sources and Mn sources mixes with Li sources, obtains persursor material 1；By Y Source, the direct physical mixed in Ba sources and Co sources, or Y sources, Ba sources and Co sources are handled using coprecipitation, obtain persursor material 2； By persursor material 1 and persursor material 2 in proportion mixed grinding, mixing, 800-1200 DEG C be calcined 5-30 hours after obtain YBaCo4O7The lithium-rich positive electrode of doping.
- 3. according to the method for claim 2, it is characterised in that：The persursor material 1 and persursor material 2 exist respectively Mixed grinding after 500 DEG C of pre-burning 4h coolings.
- 4. according to the method for claim 1, it is characterised in that：By Y sources, Ba sources, Co sources and lithium-rich oxide anode Material, which is scattered in water or ethanol, obtains suspension, and the persursor material that the suspension obtains after being evaporated is in 800-1200 DEG C of model Enclosing interior roasting 5-30 hours obtains YBaCo4O7The lithium-rich positive electrode of cladding.
- 5. according to the method for claim 4, it is characterised in that：By Li sources, Ni sources, the direct physical mixed in Co sources and Mn sources, Or the product for handling to obtain using coprecipitation by Ni sources, Co sources and Mn sources mixes with Li sources, obtains persursor material 1, before this Drive body material 1 and 5-30 hours are calcined in the range of 800-1200 DEG C, obtain described lithium-rich oxide anode material Li [Li1/3-2x/3Nix-aCo2aMn2/3-x/3-a]O2。
- 6. according to the method for claim 5, it is characterised in that：The persursor material 1 is ground after 500 DEG C of pre-burning 4h are cooled down Mill, then it is calcined 5-30 hours at 800-1200 DEG C, obtain the lithium-rich oxide anode material.
- 7. according to the method for claim 1, it is characterised in that：By Li sources, Ni sources, the direct physical mixed in Co sources and Mn sources, Or the product for handling to obtain using coprecipitation by Ni sources, Co sources and Mn sources mixes with Li sources, obtains persursor material 1, before this Drive body material 1 and 5-30 hours are calcined in the range of 800-1200 DEG C, obtain described lithium-rich oxide anode material Li [Li1/3-2x/3Nix-aCo2aMn2/3-x/3-a]O2；Adopted by Y sources, the direct physical mixed in Ba sources and Co sources, or by Y sources, Ba sources and Co sources Handled with coprecipitation, obtain persursor material 2, it is small that the persursor material 2 carries out roasting 5-30 in the range of 800-1200 DEG C When can obtain prepared YBaCo4O7Material；By lithium-rich oxide anode material Li [Li1/3-2x/3Nix- aCo2aMn2/3-x/3-a]O2And YBaCo4O7Material directly mixes, and obtains the compound lithium-rich positive electrode.
- 8. the compound lithium-rich positive electrode being prepared according to claim 1-7 any one.
- 9. lithium ion battery made of compound lithium-rich positive electrode according to claim 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710822455.5A CN107611402B (en) | 2017-09-13 | 2017-09-13 | Composite lithium-rich layered cathode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710822455.5A CN107611402B (en) | 2017-09-13 | 2017-09-13 | Composite lithium-rich layered cathode material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107611402A true CN107611402A (en) | 2018-01-19 |
| CN107611402B CN107611402B (en) | 2020-01-14 |
Family
ID=61064085
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710822455.5A Active CN107611402B (en) | 2017-09-13 | 2017-09-13 | Composite lithium-rich layered cathode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107611402B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108767245A (en) * | 2018-06-26 | 2018-11-06 | 陕西海恩新材料有限责任公司 | A kind of mixed type anode material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012204311A (en) * | 2011-03-28 | 2012-10-22 | Tokyo Institute Of Technology | Lithium-rich ternary compound, and method for manufacturing the same |
| CN103647059A (en) * | 2013-12-17 | 2014-03-19 | 惠州亿纬锂能股份有限公司 | Lithium ion battery anode material with coating layer and preparation method thereof |
| EP3086389A1 (en) * | 2013-12-17 | 2016-10-26 | Korea Electronics Technology Institute | Non-aqueous, high capacity cathode material for lithium secondary battery, and method for preparing same |
| CN106410186A (en) * | 2016-11-17 | 2017-02-15 | 天津理工大学 | Preparation method and application of lithium-rich layered oxide cathode material |
| CN106711416A (en) * | 2016-10-21 | 2017-05-24 | 东莞市迈科新能源有限公司 | Lithium-manganese-rich laminated anode material for lithium ion battery and preparation method thereof |
-
2017
- 2017-09-13 CN CN201710822455.5A patent/CN107611402B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012204311A (en) * | 2011-03-28 | 2012-10-22 | Tokyo Institute Of Technology | Lithium-rich ternary compound, and method for manufacturing the same |
| CN103647059A (en) * | 2013-12-17 | 2014-03-19 | 惠州亿纬锂能股份有限公司 | Lithium ion battery anode material with coating layer and preparation method thereof |
| EP3086389A1 (en) * | 2013-12-17 | 2016-10-26 | Korea Electronics Technology Institute | Non-aqueous, high capacity cathode material for lithium secondary battery, and method for preparing same |
| CN106711416A (en) * | 2016-10-21 | 2017-05-24 | 东莞市迈科新能源有限公司 | Lithium-manganese-rich laminated anode material for lithium ion battery and preparation method thereof |
| CN106410186A (en) * | 2016-11-17 | 2017-02-15 | 天津理工大学 | Preparation method and application of lithium-rich layered oxide cathode material |
Non-Patent Citations (4)
| Title |
|---|
| M. KARPPINEN 等: "Oxygen Nonstoichiometry in YBaCo4O7+δ: Large Low-Temperature", 《CHEMISTRY OF MATERIALS》 * |
| SUNNY HY 等: "Understanding the Role of Ni in Stabilizing the Lithium-Rich High-Capacity Cathode Material Li[NixLi(1−2x)/3Mn(2−x)/3]O2(0 ≤ x ≤ 0.5)", 《CHEMISTRY OF MATERIALS》 * |
| 任慧来 等: "YBaCo4O7的应用与发展", 《第八届全国能源与热工学术年会》 * |
| 吴承仁: "锂离子电池用富锂层状正极材料", 《化学进展》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108767245A (en) * | 2018-06-26 | 2018-11-06 | 陕西海恩新材料有限责任公司 | A kind of mixed type anode material and preparation method thereof |
| CN108767245B (en) * | 2018-06-26 | 2021-07-02 | 陕西海恩新材料有限责任公司 | Mixed type anode material and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107611402B (en) | 2020-01-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101855755B (en) | Li-Ni-based composite oxide particle powder for rechargeable battery with nonaqueous elctrolyte, process for producing the powder, and rechargeable battery with nonaqueous electrolyte | |
| CN102306779B (en) | Lithium ion battery positive electrode material lithium-enriched doped lithium molybdate and preparation method thereof | |
| CN108807926A (en) | A kind of Co/B coats nickel cobalt manganese lithium ion anode material and preparation method thereof altogether | |
| CN104134790B (en) | A kind of nickle cobalt lithium manganate is material modified and preparation method thereof and application | |
| CN104577096B (en) | Cathode material for lithium-ion battery, preparation method of cathode material and battery | |
| CN105070907A (en) | High nickel anode material, preparation method thereof and lithium ion battery | |
| CN105140492A (en) | Cobalt-nickel lithium manganate composite positive electrode material with surface wrapped by lithium zirconate and preparation method | |
| CN107492643A (en) | A kind of titanium phosphate lithium coats LiNi1/3Co1/3Mn1/3O2Positive electrode and preparation method thereof | |
| CN102332577A (en) | Lithium ion battery and anode material thereof | |
| CN104241630B (en) | Lithium nickel cobalt manganate hollow sphere as well as preparation method and application thereof | |
| CN110429268A (en) | A kind of modified boron doping lithium-rich manganese-based anode material and the preparation method and application thereof | |
| CN108550802A (en) | A kind of nickel-cobalt-manganternary ternary anode material and preparation method that Y/La doping Co/B is coated altogether | |
| CN102244260A (en) | Composite metallic-oxide-cladded lithium nickel cobalt manganese oxide anode material and preparation method thereof | |
| CN103022471B (en) | Improve the method for nickelic tertiary cathode material chemical property | |
| CN109841822A (en) | A kind of preparation method of the modified monocrystalline tertiary cathode material of lithium ion battery | |
| CN105098158B (en) | A kind of lithium-enriched cathodic material of lithium ion battery of zirconium doping and preparation method thereof | |
| CN107369815A (en) | A kind of lithium rechargeable battery composite positive pole and preparation method thereof | |
| CN108539193A (en) | Include the nucleocapsid NCM tertiary cathode materials and preparation method thereof of carbon nanotube | |
| CN106410170A (en) | Composite lithium ion battery positive material, and preparation method and lithium ion battery thereof | |
| CN111009656A (en) | Preparation method of rare earth metal doped high-nickel ternary battery positive electrode material | |
| CN102832381A (en) | Preparation method of high-voltage cathode material Lil+xMn3/2-yNil/2-zMy+zO4 of lithium ion battery with long service life | |
| CN108793254A (en) | A kind of Na0.7ZnxMnyO2The preparation method of stratified material | |
| CN115286042A (en) | Lithium-rich manganese-based positive electrode material of lithium ion battery and preparation method thereof | |
| CN109461930B (en) | Gradient-structured multi-component material for lithium ion battery and preparation method thereof | |
| CN107768628B (en) | Lithium ion battery anode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| OL01 | Intention to license declared | ||
| OL01 | Intention to license declared |