CN116768282A - High-temperature high-rate lithium cobaltate and preparation method thereof - Google Patents
High-temperature high-rate lithium cobaltate and preparation method thereof Download PDFInfo
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- CN116768282A CN116768282A CN202311022914.3A CN202311022914A CN116768282A CN 116768282 A CN116768282 A CN 116768282A CN 202311022914 A CN202311022914 A CN 202311022914A CN 116768282 A CN116768282 A CN 116768282A
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- cobalt oxide
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910052744 lithium Inorganic materials 0.000 title claims description 121
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 118
- 239000000463 material Substances 0.000 claims abstract description 138
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims abstract description 88
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000011248 coating agent Substances 0.000 claims abstract description 65
- 238000005245 sintering Methods 0.000 claims abstract description 64
- 238000000576 coating method Methods 0.000 claims abstract description 63
- 150000001875 compounds Chemical class 0.000 claims abstract description 59
- 239000000203 mixture Substances 0.000 claims abstract description 43
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 37
- 239000010941 cobalt Substances 0.000 claims abstract description 37
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000010936 titanium Substances 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 239000010416 ion conductor Substances 0.000 claims abstract description 22
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 18
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005056 compaction Methods 0.000 claims abstract description 12
- 239000007774 positive electrode material Substances 0.000 claims description 76
- 239000002245 particle Substances 0.000 claims description 55
- 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 claims description 51
- 238000000034 method Methods 0.000 claims description 34
- 239000010405 anode material Substances 0.000 claims description 25
- 238000000227 grinding Methods 0.000 claims description 20
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 19
- -1 carbonic acid compound Chemical class 0.000 claims description 19
- 238000012360 testing method Methods 0.000 claims description 15
- 239000012298 atmosphere Substances 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 238000011084 recovery Methods 0.000 claims description 14
- 238000009423 ventilation Methods 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 5
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 5
- 238000010494 dissociation reaction Methods 0.000 claims description 5
- 230000005593 dissociations Effects 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 238000002485 combustion reaction Methods 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 239000005279 LLTO - Lithium Lanthanum Titanium Oxide Substances 0.000 claims description 2
- NRJJZXGPUXHHTC-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] Chemical compound [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] NRJJZXGPUXHHTC-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical compound [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 claims description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000152 cobalt phosphate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 2
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 claims description 2
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 2
- 229910000659 lithium lanthanum titanates (LLT) Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 2
- 229910016569 AlF 3 Inorganic materials 0.000 claims 1
- 230000005347 demagnetization Effects 0.000 claims 1
- 238000010304 firing Methods 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 84
- 230000000052 comparative effect Effects 0.000 description 53
- 239000010406 cathode material Substances 0.000 description 34
- 230000008569 process Effects 0.000 description 22
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 14
- 229910052808 lithium carbonate Inorganic materials 0.000 description 14
- 230000000704 physical effect Effects 0.000 description 14
- 239000011247 coating layer Substances 0.000 description 13
- 238000003860 storage Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 238000002425 crystallisation Methods 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- 230000014759 maintenance of location Effects 0.000 description 11
- 230000008025 crystallization Effects 0.000 description 10
- 239000013078 crystal Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- 239000003607 modifier Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005253 cladding Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- VXPLXMJHHKHSOA-UHFFFAOYSA-N propham Chemical compound CC(C)OC(=O)NC1=CC=CC=C1 VXPLXMJHHKHSOA-UHFFFAOYSA-N 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 3
- 238000007580 dry-mixing Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 150000003609 titanium compounds Chemical class 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 229910017090 AlO 2 Inorganic materials 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
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- 239000003571 electronic cigarette Substances 0.000 description 2
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- 238000010902 jet-milling Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 102000004310 Ion Channels Human genes 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
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- 125000000129 anionic group Chemical group 0.000 description 1
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- 150000001869 cobalt compounds Chemical class 0.000 description 1
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- 239000002345 surface coating layer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention provides a preparation method of high-temperature high-rate lithium cobalt oxide, which comprises the steps of mixing a pre-doped cobalt source serving as a raw material with a modified material, performing first sintering, grading and crushing, mixing with a first coating cobalt-containing compound, a titanium-containing compound and an aluminum-containing compound, performing second sintering, grading and crushing a second sintering product, mixing with a mixture of a nano fast ion conductor and a fluoride, and performing third sintering to obtain the lithium cobalt oxide material which has good high-temperature performance, good rate performance and higher compaction density and can meet the requirement of high-voltage application.
Description
Technical Field
The invention belongs to the field of lithium ion battery materials, and particularly relates to high-temperature high-rate lithium cobaltate and a preparation method thereof.
Background
The lithium cobaltate is used as the anode material of the lithium ion battery which is commercialized earliest and is widely applied to the battery fields of mobile phones, digital codes and the like. In addition, the fields of electronic cigarettes, unmanned aerial vehicles and the like which are currently emerging also begin to use lithium ion batteries which use lithium cobaltate as a positive electrode material as a power source.
Along with the continuous expansion of the application range of lithium cobaltate, the requirements of lithium cobaltate batteries are continuously updated and improved, and the requirements are mainly embodied in the following aspects:
(1) At present, the energy density requirement on lithium cobaltate batteries is higher and higher, and most batteries of high-end electronic products are updated to be battery cores with the charging cut-off voltage of 4.45V and higher.
(2) At present, when the battery is exhausted, the full charge takes at least more than 2 hours, and whether the battery can be quickly fully charged in a short time is one of the most concerned problems. The new application field of the lithium cobaltate battery needs continuous high-current charge and discharge to meet the use requirement of the lithium cobaltate battery, so that the lithium cobaltate battery has higher requirement on high-current charge and discharge capability (namely multiplying power performance).
(3) The new application fields of lithium cobaltate batteries such as electronic cigarettes and unmanned aerial vehicles not only require that lithium cobaltate has excellent multiplying power performance at normal temperature, but also require that the multiplying power lithium cobaltate can be suitable for a higher temperature environment and has better circulation and storage performance at high temperature.
The patent publication numbers CN 113247963B and CN 113247964B of the inventor apply for high-compaction high-rate high-voltage lithium cobalt oxide positive electrode materials, and the disclosed materials can meet the requirements of the high-rate high-compaction high-voltage lithium cobalt oxide positive electrode materials.
However, with the appearance of new application fields of lithium cobaltate batteries, the lithium cobaltate battery has higher requirements on the high-temperature performance of high-voltage high-magnification lithium cobaltate products, and meanwhile, the compaction density of the materials is considered, so that new problems are faced in material design, and the lithium cobaltate materials on the market and the lithium cobaltate materials disclosed in the prior art are difficult to simultaneously meet the performance requirements of high temperature, high voltage and high magnification, and have higher compaction density.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of high-temperature high-rate lithium cobaltate.
To achieve the above object, the present invention proposes the following solution:
the inventor researches and discovers that the use of lithium cobaltate as a positive electrode active material of a high-temperature, high-voltage and high-multiplying power lithium ion battery has very important influences on aspects such as particle size, crystal morphology, doping and coating, micro powder control, residual lithium control and the like, and precise and complex regulation and control are needed. When the particle size becomes large, the discharge efficiency is lowered under the condition of high-rate discharge; when the particle size becomes smaller, the processability becomes worse and the safety and cycle performance are also lowered under high-rate discharge. The crystal morphology can be mainly divided into polycrystal and monocrystal, and different morphologies have intricate influence on the comprehensive performances of high temperature, high voltage and high multiplying power of lithium cobaltate. The lithium cobaltate with polycrystalline morphology has better multiplying power performance due to small primary particles, but has larger specific surface, is easy to cause electrochemical side reaction between the material and electrolyte under high voltage, and causes the exposed fresh inner surface to continuously react with the electrolyte to generate other phases due to the fact that agglomerate particles are broken, pulverized and separated in the circulation process, so that the electric performance is deteriorated. This can effectively solve the above-mentioned problems by preparing a lithium cobaltate positive electrode material having a high degree of single crystallization. Materials with a high degree of single crystallization have a small specific surface area, and therefore have reduced side reactions with the electrolyte, and thus have improved recycling properties. The high-temperature, high-voltage and high-multiplying power performances of the lithium cobaltate material are balanced, the doping amount of Al is increased, and the balance of comprehensive performances is realized by adopting an anionic element and a fast ion conductor material for coating. In addition, the reduction of the micro powder content of the material and the control of the residual lithium content are also beneficial to the improvement of the high-temperature performance of the material.
Through continuous and intensive innovation research, the product is controlled to have the particle size D50 of 6.0-9.0 mu m, the single crystallization degree is high, the doping and cladding are reasonably optimized, the micro powder amount and the residual lithium amount are reasonably controlled, the performance requirements of the lithium cobaltate material on high temperature, high voltage and high multiplying power can be simultaneously met, and meanwhile, the compaction density of the material can be considered.
Specifically, a preparation method of a high-temperature high-rate lithium cobalt oxide positive electrode material is provided, which comprises the following steps:
(1) Will be pre-doped with element M 1 Cobalt source, lithium source, M-containing 2 Compounds of (C) containing M 3 Compounds of (2) and M-containing compounds 4 The compound of (2) is mixed to obtain a primary mixture; the M is 1 One or more of Al, ni and Mn; m is M 2 One or more than two selected from La, gd and Y; m is M 3 One or more than two of Ti, nb and V; m is M 4 One or more than two of B, mg and Li;
(2) Performing first sintering on the primary mixture, and then crushing and grading to obtain a first-sintering crushed graded material;
(3) The first-fired crushed classified material and the first coating are mixed to obtain a secondary mixture; the first coating is selected from one or more than two of cobalt-containing compounds, titanium-containing compounds and aluminum-containing compounds;
(4) Performing secondary sintering on the secondary mixture, and then crushing and grading to obtain a secondary-sintering crushed graded material;
(5) Mixing the secondary-burning crushed classified material with a second coating material to obtain a tertiary mixture; the second coating is a mixture of a nano fast ion conductor and fluoride;
(6) And (3) carrying out third sintering on the tertiary mixture, and carrying out dissociation, demagnetizing and sieving to obtain the high-temperature high-rate lithium cobalt oxide positive electrode material.
Preferably, the pre-doping element M 1 Is selected from the group consisting of pre-doping element M 1 One or more of cobalt oxyhydroxide, cobalt hydroxide, cobalt tetraoxide, cobalt nitrate, cobalt carbonate, cobalt chloride, cobalt phosphate, cobalt acetylacetonate and cobalt sulfate. The M is 1 The doping amount of the lithium cobalt oxide anode material is 6000-15000 mg/kg of the weight of the lithium cobalt oxide anode material. The invention adopts the material containing the pre-doping element M 1 Cobalt salts of (Al, ni, mn) as important raw materials, pre-doped with element M 1 Is an additive. In lithium cobalt oxide synthesized from the raw materialM under high voltage and high temperature conditions 1 The additive mainly has the functions of stabilizing the structure, improving the thermal stability of the anode material and increasing the charge-discharge window. Because of higher requirements for high voltage and high temperature performance of the synthesized product, M 1 The doping amount of the lithium cobalt oxide material is larger, the preferable range is 6000-15000 mg/kg, when the doping amount is too high, the capacity and the multiplying power performance of the lithium cobalt oxide material are reduced, and when the doping amount is too low, the high-voltage and high-temperature performance cannot meet the requirements. At the same time due to M 1 If the doping amount of the cobalt oxide is large, if the wet pre-doping method in the cobalt oxide is not adopted, but the dry mixing is adopted when one-time batching is adopted, the pre-doping element M in the sintered product can be caused 1 The distribution of (c) is uneven, and segregation occurs on a microscopic scale.
Preferably, the M-containing 2 Is selected from one or more of La, gd, and Y hydroxide, oxyhydroxide, oxide, carbonic acid compound, and acetic acid compound; the M is 2 The doping amount of the lithium cobalt oxide anode material is 100-2000 mg/kg. Due to doping of metal element M 2 Is larger (average ratio M) 1 Large) and all have significantly larger ionic radii than Co 3+ Is relatively difficult to enter the lithium cobaltate lattice, so the doping amount is relatively small. In general, in the preparation process of lithium cobaltate, doping is completed in a primary sintering process, and cladding is completed in a secondary sintering process, but the invention selects M with large ion radius 2 The elements are added during primary sintering, so that the effect of doping and surface coating is achieved, and the elements and other coating substances added during secondary sintering have the effect of double protection on lithium cobaltate.
In order to obtain lithium cobaltate with high single crystallization degree, the invention adds M in the step (1) 3 Compounds of (2) and M-containing compounds 4 Is a compound of (a). Preferably, the M-containing 3 The compound is selected from one or more of hydroxide, oxyhydroxide, oxide, carbonic acid compound and acetic acid compound of Ti, nb and V, wherein M is 3 The doping amount of the lithium cobalt oxide anode material is 100-2000 mg/kg of the weight of the lithium cobalt oxide anode material. As a preferenceThe M contains 4 The compound is one or more selected from B, mg, li hydroxide, hydroxyl oxide, carbonic acid compound and acetic acid compound, and contains M 4 The addition amount of the compound is 100-2000 mg/kg of the weight of the lithium cobalt oxide positive electrode material.
In the first sintering process, the pre-doping element M can be adjusted 1 Doping metal element M 2 Modifier M 3 And modifier M 4 The addition amount, the type and the combination of the lithium cobalt oxide particles are used for controlling the growth of the lithium cobalt oxide particles, so that the size, the fusion degree and the high single-crystallization structure formed by fusion of the lithium cobalt oxide particles are regulated and controlled, and the crystal morphology, the specific surface area and the compaction condition of the lithium cobalt oxide material can be further regulated and controlled, so that the effect of optimizing the ion transmission path and channel is achieved, and the high-temperature, high-voltage and high-rate performance of the material is improved. Pre-doping element M 1 Doping metal element M 2 Modifier M 3 And modifier M 4 The capacity of the lithium cobaltate material is reduced due to the excessive doping amount, and the optimization effect cannot be achieved due to the insufficient doping amount.
In addition, the research shows that the layered structure of lithium cobaltate expands and contracts correspondingly during the process of extracting and inserting lithium ions, and internal stress and strain are generated. When charged to 4.45V and higher, the layered structure of lithium cobaltate is insufficient to withstand large stress changes to undergo irreversible phase transformation, even collapse of the material structure. Pre-doping element M 1 Doping metal element M 2 Modifier M 3 And modifier M 4 Can enter into the crystal lattice of lithium cobalt oxide, and can play a role in stabilizing the crystal lattice of lithium cobalt oxide when lithium ions in the lithium cobalt oxide are extracted.
Preferably, the molar ratio n (Li): n (Co) of the lithium element of the lithium source to the cobalt element of the cobalt source is 1.1-1.0:1.
Preferably, in step (2), the first sintering includes: oxygen mass fraction in sintering atmosphere is 20% -100%, ventilation is 21-30 m 3 Under the condition of/h, the primary mixture is heated to 720-780 ℃ from the temperature, is kept for 2-6 hours, is then heated to 950-1200 ℃ and is kept for 8-12 hoursWhen (1).
Preferably, the cobalt-containing compound is selected from Co (OH) 2 One or more of cobalt oxyhydroxide, cobaltous hydroxide and cobaltosic oxide; the cobalt-containing compound is 5000-40000 mg/kg of the weight of the primary sintering material; when the consumption is too high, the content of residual cobalt in the product is too high to reduce the capacity, and when the consumption is too low, the content of residual lithium is too high to influence the high-temperature performance of the product.
Preferably, the titanium-containing compound is selected from TiO 2 One or two of titanium hydroxide; ti in the titanium-containing compound is 100-3000 mg/kg of the weight of the primary sintering material; when the usage amount is too high, the capacity of the product is reduced, and when the usage amount is too low, the content of residual lithium is too high, so that the high-temperature performance and the rate capability of the product are affected.
Preferably, the aluminum-containing compound is selected from the group consisting of Al 2 O 3 One or two of aluminum hydroxide; al in the aluminum-containing compound is 200-3000 mg/kg of the weight of the primary sintering material; when the usage amount is too high, the capacity of the product is reduced, and when the usage amount is too low, the content of residual lithium is too high, so that the high-temperature performance and the rate capability of the product are affected.
Preferably, the nano fast ion conductor is selected from one or more of nano Lithium Aluminum Titanium Phosphate (LATP), nano Lithium Lanthanum Zirconium Oxide (LLZO) and nano Lithium Lanthanum Titanate (LLTO); the weight of the nano fast ion conductor is 200-3000 mg/kg of the weight of the primary sintering material; when the usage is too high, the capacity of the product is reduced, and when the usage is too low, the high-temperature performance, the rate capability and the high-voltage performance of the product are affected.
Preferably, the fluoride is selected from LiF, alF 3 、YF 3 、TiF 4 One or two or more of them; f in the fluoride is 200-3000 mg/kg of the weight of the primary sintering material. When the usage is too high, the capacity of the product is reduced, and when the usage is too low, the high-temperature performance and the high-voltage performance of the product are affected.
In the invention, the lithium cobaltate sintered crushed grading material before cladding is a doped lithium cobaltate anode material matrix, and the surface residual lithium amount is 100-600 mg/kg; and (3) reducing the residual lithium of the coated lithium cobalt oxide positive electrode material obtained in the step (4) to 10-40 mg/kg. The book is provided withThe matrix material before coating is particles synthesized by a high-temperature solid phase method, and the radial Li of the particles + There is a concentration gradient from the region away from the surface to the surface region of the particle, li + The concentration gradually increases, and the surface is rich in Li + In this state, these surface free lithium is called residual lithium.
The residual lithium content on the surface of the doped lithium cobalt oxide matrix is preferably 100-600 mg/kg; if the residual lithium is high, the residual lithium directly enters a finished product, and is easy to generate side reaction with electrolyte under the test condition of high temperature and high voltage due to high activity of the residual lithium, so that gas expansion is caused, and the high-temperature storage performance and the cycle performance of the battery are deteriorated. Therefore, in the coating process, the invention adds the lithium cobalt oxide which is doped with the lithium cobalt oxide and can consume the surplus Li + The additive of (a) contains cobalt compound, titanium compound and aluminum compound. Through heat treatment, li + And the cobalt-containing compound reacts with the cobalt-containing compound to form active lithium cobalt oxide, and part of the cobalt-containing compound is subjected to heat treatment to form an oxide coating layer on the surface of the particles. Li consumption by cobalt-containing compounds + Is the process of (1), li + Redistributing in the doped lithium cobaltate matrix particles and tending to a stable state, so as to realize accurate regulation and control of n (Li)/n (Co) in the material; in addition, cobalt-containing compounds absorb Li + Not only can stabilize the internal structure of the particles, but also can form a layer of oxide coating layer of cobalt on the surfaces of the particles to isolate Co at high potential 4+ Contact with the electrolyte can improve the surface stability of the particles. In addition, the coating contains titanium compound and aluminum compound and Li which is rich in surface in doped lithium cobalt oxide by heat treatment + Can react to form Li 4 Ti 5 O 12 And Li (lithium) 2 AlO 2 The two coating layers contain Li ions, have higher chemical diffusion coefficient and structural stability, hardly change the crystal structure in the charge and discharge process, are excellent coatings, reduce material impedance after coating, and improve high-temperature performance and rate performance.
The nano fast ion conductor is coated on the surface of the lithium cobaltate anode material, on one hand, the nano fast ion conductor coating layer is used as a protective layer to isolate the electrolyte from directly contacting with the anode material, so that related side reactions, such as cobalt dissolution reduction, formation of thinner SEI film and the like, are reduced, and the electrochemical stability of the material is improved; on the other hand, the nano fast ion conductor coating layer has high ion conductivity and excellent thermal stability, can obviously improve the conductivity of the material, reduce the internal resistance and realize the fast charge and discharge and high-temperature cycle performance of the lithium ion battery.
The fluoride has strong electronegativity and very stable fluoride, so that after being coated and modified by fluoride, the fluoride has obviously improved circulation and high-temperature storage performance under high voltage, and the irreversible phase change and gas production phenomena are effectively inhibited.
From the above analysis, it was found that the coating of cobalt-containing compound consumes excessive Li + And the double effect of forming an oxide coating layer is beneficial to the high-voltage and high-temperature performance of the lithium cobaltate material; the use of the coating containing titanium compound and aluminum compound consumes surplus Li + And formation of Li 4 Ti 5 O 12 And Li (lithium) 2 AlO 2 The double functions of the coating layer are beneficial to the high-temperature performance and the rate capability of the lithium cobaltate material; the coating of the nano fast ion conductor is beneficial to the high-temperature performance and the rate capability of the lithium cobaltate material; the fluoride coating is also beneficial to the high voltage performance and high temperature performance of the lithium cobaltate material. By using these coating agents in combination, the combined benefits and synergistic effects of the coating agents can be fully exerted, and the material performance can be significantly improved.
The performance of the material can be further optimized by optimizing the dosage of the cobalt-containing compound, the titanium-containing compound, the aluminum-containing compound, the nano fast ion conductor and the fluoride of the coating, and when the addition of the coating is too small, a complete coating layer cannot be formed on the surface of the material, and more lithium remains on the surface of the material can be caused, so that the performance of the material is affected; too much addition of these coatings can result in too thick coating layers, affecting the electrical conductivity of the material and degrading the rate performance and cycle performance of the material.
As a further preferred aspect, the coating in steps (3) to (6) is a dry coating. In the secondary mixing and the tertiary mixing, materials are uniformly dispersed by virtue of shearing stress and other acting forces of a high-speed mixer, a sintered product is tightly combined with a coating, and the dry coating is realized after secondary sintering and tertiary sintering. According to the invention, a solid solution can be formed between the coating agent and the surface of the lithium cobaltate by adopting a dry coating method, so that the coating agent is favorably and tightly and uniformly combined with the uneven surface of the lithium cobaltate particles, and a good coating effect is achieved. In addition, the cobalt-containing compound, the titanium-containing compound and the aluminum-containing compound in the coating agent can react with residual lithium on the surface of the lithium cobaltate, and a certain chemical reaction power is provided to promote the close and uniform combination of the coating agent and the surface of the lithium cobaltate, and meanwhile, the cobalt-containing compound, the titanium-containing compound and the aluminum-containing compound also have good compatibility between the finally formed oxide and the lithium cobaltate, so that the close and uniform combination of the coating layer and the lithium cobaltate particles with uneven surfaces is further promoted.
Preferably, in step (4), the second sintering includes: the oxygen mass fraction in the sintering atmosphere is 20-100%, and the ventilation is 10-20 m 3 And (3) under the condition of/h, the secondary mixture is kept at 900-980 ℃ for 8-12 hours, and then kept at 800-850 ℃ for 2-4 hours. In order to realize that the coating can be more tightly coated on the surfaces of the substrate materials with different particle diameters, the secondary sintering process of the invention is carried out at 800-850 ℃ for 2-4 hours in the cooling process, thus promoting the reaction between the substrate materials with different particle diameters and the coating materials on the surfaces, and enabling the coating layers to absorb different stresses generated by primary particles; meanwhile, the coating material is tightly attached to the surfaces of the base materials with different particle sizes through high-temperature atomic diffusion, so that the coating material is prevented from falling off due to expansion/contraction of the volumes of the base materials with different particle sizes in the electrochemical circulation process, the composite compound in the coating material is connected with the base materials with different particle sizes through chemical bonds, and the bonding strength between the coating structure and the base materials with different particle sizes is reinforced.
Preferably, the secondary sintering and the tertiary sintering are performed at a temperature not higher than that of the primary sintering in order not to affect the degree of single crystallization of the primary sintered product during the whole preparation process. The third sintering includes: the oxygen mass fraction in the sintering atmosphere is 20-100%, and the ventilation is 10-20 m 3 Bars of/hAnd under the piece, preserving the heat for 8-12 hours at 770-870 ℃.
Preferably, the particle size of the one-shot pulverized graded material is as follows: d (D) 0 ≥ 0.5μm，D 50 At 4.5-7.5 μm.
Preferably, the particle size of the two-fired pulverized classified material is as follows: d (D) 0 ≥ 0.5μm，D 50 At 6.0-9.0 μm. Most by strictly controlling the particle size of the material so that material D 0 The particle size is more than or equal to 0.5 mu m, and adverse effects of micro powder with the particle size smaller than 0.5 mu m on products are avoided, so that the safety performance and the high-temperature cycle performance of the positive electrode material in the use process can be improved, and the compaction density of the positive electrode material in the use process can be improved.
Preferably, in the step (2) or the step (4), the pulverizing and classifying includes: firstly, adopting a jaw crusher and a twin-roll mill for coarse crushing, and then adopting an environment-friendly fluidized bed type totally-enclosed supersonic jet crushing integrated machine for crushing and grading. Jaw crusher and twin-roll mill belong to coarse crushing links, and can crush massive materials into rice grains; then an environment-friendly fluidized bed type totally-enclosed supersonic jet milling integrated machine is adopted to mill and grade the materials into micron qualified materials, and micropowder (fine powder with particle diameter smaller than 0.5 μm) generated in the process is collected by a pulse ash-cleaning dust collector and does not enter the process of secondary batching and mixing, so that the control of micropowder in the finished product is facilitated from the source. The organic combination of the three crushers can improve the production efficiency and reduce the micro powder content of the product. The environment-friendly fluidized bed type totally-enclosed supersonic jet milling integrated machine is adopted for milling and grading, and the equipment is characterized by integrating the machine, being totally-enclosed, dust-free and environment-friendly; the automation degree is high, and remote control can be realized; the device can automatically feed materials, and integrates the functions of crushing, automatic grading, finished product collection and automatic discharging into a whole.
Preferably, in the step (2), the parameters of crushing and classifying by using the environment-friendly fluidized bed type totally-enclosed supersonic jet crushing integrated machine are as follows: the grinding air pressure is 0.56-0.65 MPa, the frequency of a grading motor is 15-33 Hz, the frequency of a feeding motor is 7-11 Hz, and the grinding body pressure is-0.9 to-2.0 KPa.
Preferably, in the step (4), the parameters of the crushing and classifying by using the environment-friendly fluidized bed type totally-enclosed supersonic jet crushing integrated machine are as follows: the grinding air pressure is 0.35-0.41 MPa, the frequency of a grading motor is 25-31 Hz, the frequency of a feeding motor is 6-14 Hz, and the grinding body pressure is-4.0 to-5.4 KPa.
The invention also provides the lithium cobalt oxide positive electrode material prepared by the preparation method, wherein the positive electrode material is a single crystal material, and D of the positive electrode material 0 0.5 μm (more preferably D) 0 ≥1.5μm），D 50 6.0-9.0 mu m; the specific surface area is 0.15-0.45 m 2 /g; the residual lithium on the surface is 10-40 mg/kg; the compaction density is 3.7-3.9 g/cm 3 。
Preferably, the discharge capacity of the full battery assembled by the positive electrode material at 0.2C is more than or equal to 180mAh/g in the voltage test range of 25 ℃ and 3.0-4.45V, and the ratio of the discharge capacity under the conditions of 0.2C charge and 20C discharge to the discharge capacity under the condition of 0.2C charge and discharge is not less than 95.0 percent; the cycle of 4C/5A pulse discharge at 45 ℃ is 600 weeks or more and 80 percent (namely, the cycle under 4C charge and 5A pulse discharge conditions); the thickness expansion rate is less than or equal to 8% at 85 ℃ and 4 hours (namely, the thickness expansion rate is placed at 85 ℃ for 4 hours), and the capacity recovery rate (the ratio of the capacity after being placed at 85 ℃ for 4 hours to the capacity before the test) is more than or equal to 94.0%.
In the present invention, M 1 Higher doping levels of elements and pre-doping of precursors, M 2 Dual effect of element doping and surface coating, M-containing 3 Compounds and M-containing compounds 4 The control of the single crystallization morphology of the compound, the control of the micro powder content, the dual effects of the coating of the cobalt-containing compound, the use of the coating of the titanium-containing compound and the aluminum-containing compound, the coating of the nano fast ion conductor and the fluoride, and the combination of the technical means can ensure that the high temperature performance of the lithium cobaltate material can meet the requirements; the single crystallization degree is improved, the doping and cladding are reasonably optimized, the micro powder amount and the residual lithium amount are reasonably controlled, and the technical means can ensure that the high voltage performance of the lithium cobaltate material can meet the requirements; coating of nano fast ion conductor with proper particle size, titanium-containing compound and aluminum-containing compoundThe technical means ensure that the high rate performance of the lithium cobaltate material can meet the requirements; particle size D of lithium cobaltate twice-fired crushed graded material 0 ≥ 0.5μm，D 50 At 6.0-9.0 mu m, the particles are uniform, the oversized and undersized particles can not appear, the single crystallization degree of the product is improved, and the technical means ensure that the compaction density of the material can reach 3.7g/cm 3 ～3.9g/cm 3 Higher level.
Compared with the prior art, the invention has the following beneficial effects:
1. the lithium cobaltate anode material prepared by the method can meet the performance requirements of high temperature, high voltage and high multiplying power at the same time, and has higher compaction density.
2. The lithium cobalt oxide anode material prepared by the invention has uniform chemical components and phase components, easy control of morphology and granularity and excellent electrochemical performance.
3. The preparation method disclosed by the invention is simple and convenient to operate, has higher production efficiency, has low equipment requirement, is simple and easy to control in synthesis process, and has high product consistency.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is an SEM image of a high-voltage positive electrode material of high-temperature-rate lithium cobaltate prepared by the method of example 1 of the present invention.
Fig. 2 is an SEM image of a high-voltage positive electrode material of high-temperature-rate lithium cobaltate prepared by the method of example 2 of the present invention.
Detailed Description
The invention will be described more fully hereinafter with reference to the accompanying drawings and preferred embodiments in order to facilitate an understanding of the invention, but the scope of the invention is not limited to the following specific embodiments.
Example 1:
the invention relates to a high-temperature multiplying power lithium cobalt oxide high-voltage positive electrode material, wherein D 0 2.21 μm, D 50 6.84 μm; specific surface area of 0.33 m 2 /g; the residual lithium content on the surface is 21mg/kg; a compacted density of 3.75g/cm 3 . An SEM image of the material of this example is shown in fig. 1. As can be seen from fig. 1, the material particles are uniform, no oversized or undersized particles are present, and the product has a high degree of single crystallization. The full battery assembled by the material is tested to have a 0.2C discharge capacity of 182.0mAh/g and a 20C/0.2C rate performance of 97.1% in a voltage test range of 25 ℃ and 3.0V-4.45V; pulse discharge cycle 600 weeks capacity retention rate at 45 deg.c, 4C charge, 5A pulse discharge condition is 82.3%;85 DEG C&The thickness expansion rate at 4 hours was 6.5%, and the capacity recovery rate was 95.9%.
The preparation method of the high-temperature rate lithium cobaltate high-voltage positive electrode material comprises the following steps:
(1) Particle diameter D 50 3.5 mu m pre-doped cobaltosic oxide, lithium carbonate and Y 2 O 3 、TiO 2 And Mg (OH) 2 And (3) batching, and then mixing by adopting a coulter type mixer to obtain a primary mixture. The molar ratio of the lithium element in the lithium carbonate to the cobalt element in the cobaltosic oxide is n (Li): n (Co) =1.05:1, the pre-doping element Al in the cobaltosic oxide is 11000 Mg/kg of the weight of the lithium cobalt oxide positive electrode material, the adding amount of Y is 1000 Mg/kg of the weight of the lithium cobalt oxide positive electrode material, the adding amount of Ti is 500Mg/kg of the weight of the lithium cobalt oxide positive electrode material, and the adding amount of Mg is 1500Mg/kg of the weight of the lithium cobalt oxide positive electrode material.
(2) Placing the uniformly mixed primary mixture obtained in the step (1) in an atmosphere with the oxygen mass fraction of 23% and the ventilation of 25m 3 And under the condition of/h, the temperature is raised to 750 ℃ from room temperature, the temperature is kept for 4 hours, then the temperature is raised to 1050 ℃, the temperature is kept for 10 hours, and the materials are naturally cooled along with the furnace. Coarse crushing the material after primary sintering by a jaw crusher and a twin-roll mill, and crushing and grading by an environment-friendly fluidized bed type totally-enclosed supersonic jet crushing integrated machine to obtain a primary-sintering crushed graded material. Particle size D of one-time baking crushed graded material 0 1.2 μm, D 50 5.5 μm. The parameters for comminution and classification are as follows: the grinding air pressure is 0.6 MPa, the frequency of a grading motor is 24Hz, the frequency of a feeding motor is 9Hz, and the pressure of a grinding body is-1.5 KPa.
(3) And (3) mixing the primary-burned crushed classified material obtained in the step (2) with the coating 1, and then mixing at a high speed to obtain a secondary mixture. The coating 1 is Co (OH) 2 、TiO 2 、Al 2 O 3 Wherein Co (OH) 2 15000 mg/kg of the weight of the primary sintered product; tiO (titanium dioxide) 2 Ti in the alloy is 500 mg/kg of the weight of the primary sintered product; al (Al) 2 O 3 The Al content in the alloy is 900 mg/kg of the weight of the primary sintered product.
(4) The obtained secondary mixture was placed in an atmosphere having an oxygen mass fraction of 23% and a ventilation of 15m 3 And under the condition of/h, heating from room temperature to 950 ℃, preserving heat for 10 hours, then cooling to 820 ℃, preserving heat for 3 hours, and then naturally cooling along with a furnace. Coarse crushing the material after secondary sintering by a jaw crusher and a twin-roll mill, and crushing and grading by an environment-friendly fluidized bed type totally-enclosed supersonic jet crushing integrated machine to obtain a secondary-sintering crushing graded material. Particle size D of the secondary combustion crushed graded material 0 2.20 μm, D 50 6.80 μm. The parameters for the comminution and classification are as follows: the grinding air pressure is 0.38MPa, the frequency of a grading motor is 28Hz, the frequency of a feeding motor is 10Hz, and the pressure of a grinding body is-4.7 KPa.
(5) And (3) mixing the twice-burned crushed classified material obtained in the step (4) with the coating 2, and then carrying out high-speed mixing to obtain a three-time mixture. The coating 2 is nano fast ion conductor LLZO and fluoride LiF, wherein LLZO is 1000 mg/kg of the weight of the primary sintering product; f in LiF is 1000 mg/kg of the weight of the primary sintered product.
(6) Placing the obtained three times mixture in an atmosphere with oxygen mass fraction of 25% and ventilation of 12m 3 And under the condition of/h, the temperature is raised to 820 ℃ from room temperature, the temperature is kept for 8 hours, and then the mixture is naturally cooled along with a furnace. And then carrying out high-speed dissociation on the three-time sintered material to obtain a three-time sintered dissociated material, and then carrying out demagnetizing and sieving to obtain the high-temperature rate lithium cobalt oxide positive electrode material. Particle size D of the triple-fired dissociation material 0 2.21 μm, D 50 6.84 μm.
Example 2:
the invention relates to a high-temperature multiplying power lithium cobalt oxide high-voltage positive electrode material, wherein D 0 2.28 μm, D 50 7.38 μm; specific surface area of 0.28 and 0.28 m 2 /g; the residual lithium content on the surface is 25mg/kg; a compacted density of 3.80 g/cm 3 . An SEM image of the material of this example is shown in fig. 2. As can be seen from fig. 2, the material particles are uniform, no oversized or undersized particles are present, and the product has a high degree of single crystallization. The discharge capacity of 0.2C is 181.5 mAh/g and the multiplying power performance of 20C/0.2C is 96.5% in the voltage test range of 3.0V-4.45V at 25 ℃ of the full battery assembled by the material; pulse discharge cycle 600 weeks capacity retention rate at 45 ℃ under 4C charging and 5A pulse discharge conditions is 82.8%;85 DEG C&The thickness expansion rate at 4 hours was 6.0% and the capacity recovery rate was 95.8%.
The preparation method of the high-temperature rate lithium cobaltate high-voltage positive electrode material comprises the following steps:
(1) Particle diameter D 50 3.7 mu m pre-doped cobaltosic oxide, lithium carbonate and La 2 O 3 、Nb 2 O 5 And B 2 O 3 And (3) batching, and then mixing by adopting a coulter type mixer to obtain a primary mixture. Wherein the molar ratio of lithium element in lithium carbonate to cobalt element in cobaltosic oxide is n (Li): n (Co) =1.07:1, the pre-doping element Al in the cobaltosic oxide is 10000 mg/kg of the weight of the lithium cobalt oxide positive electrode material, the addition amount of La is 1500 mg/kg of the weight of the lithium cobalt oxide positive electrode material, the addition amount of Nb is 700 mg/kg of the weight of the lithium cobalt oxide positive electrode material, and the addition amount of B is 1300 mg/kg of the weight of the lithium cobalt oxide positive electrode material.
(2) Placing the uniformly mixed primary mixture obtained in the step (1) in an atmosphere with an oxygen mass fraction of 40% and a ventilation of 22m 3 And under the condition of/h, the temperature is raised to 730 ℃ from room temperature, the temperature is kept for 5 hours, then the temperature is raised to 1075 ℃, the temperature is kept for 9 hours, and the furnace is naturally cooled. Coarse crushing the primary sintered material in jaw crusher and double-roller crusher, and crushing and grading in environment friendly fluidized bed type fully closed supersonic airflow crushing machine to obtain one product And (5) sintering and crushing the grading materials. Particle size D of one-time baking crushed graded material 0 1.4 μm, D 50 5.9 μm. The parameters for comminution and classification are as follows: the grinding air pressure is 0.6 MPa, the frequency of a grading motor is 24Hz, the frequency of a feeding motor is 9Hz, and the pressure of a grinding body is-1.2 KPa.
(3) And (3) mixing the primary-burned crushed classified material obtained in the step (2) with the coating 1 according to a certain proportion, and then mixing by adopting a high-speed mixer to obtain a secondary mixture. The coating 1 is Co (OH) 2 、TiO 2 、Al 2 O 3 . Wherein Co (OH) 2 40000 mg/kg by weight of primary sintered product; tiO (titanium dioxide) 2 Ti in the alloy is 1000 mg/kg of the weight of the primary sintered product; al (Al) 2 O 3 The Al content in the alloy is 1500 mg/kg of the weight of the primary sintered product.
(4) The obtained secondary mixture was placed in an atmosphere having an oxygen mass fraction of 40% and a ventilation of 12m 3 And under the condition of/h, heating from room temperature to 930 ℃, preserving heat for 11 hours, then cooling to 820 ℃, preserving heat for 3 hours, and then naturally cooling along with a furnace. Coarse crushing the material after secondary sintering by a jaw crusher and a twin-roll mill, and crushing and grading by an environment-friendly fluidized bed type totally-enclosed supersonic jet crushing integrated machine to obtain a secondary-sintering crushing graded material. Particle size D of the secondary combustion crushed graded material 0 2.22 μm, D 50 7.21 μm. The parameters for the comminution and classification are as follows: the grinding air pressure is 0.38MPa, the frequency of a grading motor is 28Hz, the frequency of a feeding motor is 10Hz, and the pressure of a grinding body is-4.7 KPa.
(5) And (3) mixing the twice-burned crushed classified material obtained in the step (4) with the coating 2, and then carrying out high-speed mixing to obtain a three-time mixture. The coating 2 is nano fast ionic conductors LATP and YF 3 Wherein LATP is 1500 mg/kg of the weight of the primary sintered product; YF (Yf) 3 F in (2) is 200mg/kg of the weight of the primary sintered product.
(6) Placing the obtained three times mixture in an atmosphere with oxygen mass fraction of 50% and ventilation of 10m 3 And under the condition of/h, the temperature is raised to 860 ℃ from room temperature, the temperature is kept for 10 hours, and then the mixture is naturally cooled along with a furnace. Then the tertiary sintered material is dissociated at high speed to obtain the tertiary sintered dissociationAnd (3) carrying out material removal, magnetism removal and sieving to obtain the high-temperature rate lithium cobalt oxide positive electrode material. Particle size D of the triple-fired dissociation material 0 2.28 μm, D 50 7.38 μm.
As can be seen from examples 1 and 2, materials having similar physical and electrochemical properties can be prepared in the different examples, although the raw materials and the process parameters used in the preparation process are changed.
Example 3:
the difference between this example and example 1 is only that in step (1), the pre-doped element Al in the tricobalt tetraoxide is 15000 mg/kg of the weight of the lithium cobaltate cathode material.
D of the obtained lithium cobalt oxide 0 2.31 μm, D 50 6.93 μm; specific surface area of 0.32 m 2 /g; the residual lithium content on the surface is 23mg/kg; the compacted density is 3.77 g/cm 3 . The full battery assembled by the material is tested to have a 0.2C discharge capacity of 182.2mAh/g and a 20C/0.2C rate performance of 97.0% in a voltage test range of 25 ℃ and 3.0V-4.45V; pulse discharge cycle 600 weeks capacity retention rate at 45 deg.c, 4C charge, 5A pulse discharge condition is 81.9%;85 DEG C&The thickness expansion rate at 4 hours was 6.1% and the capacity recovery rate was 95.2%.
Example 4
The difference between this example and example 1 is only that in step (1), the pre-doped element Al in tricobalt tetraoxide is 6000 mg/kg of the weight of the lithium cobaltate positive electrode material.
D of the obtained lithium cobalt oxide 0 2.15 μm, D 50 6.73 μm; specific surface area of 0.34 m 2 /g; the residual lithium content on the surface is 25mg/kg; the compacted density is 3.73 g/cm 3 . The full battery assembled by the material is tested to have a 0.2C discharge capacity of 182.1mAh/g and a 20C/0.2C rate performance of 97.2% in a voltage test range of 25 ℃ and 3.0V-4.45V; pulse discharge cycle 600 weeks capacity retention rate at 45 deg.c, 4C charge, 5A pulse discharge condition is 82.5%;85 DEG C&The thickness expansion rate at 4 hours was 6.3%, and the capacity recovery rate was 95.4%.
Example 5
The difference between this embodiment and embodiment 1 is that in step (1), the pre-doping element in the tricobalt tetraoxide is Ni.
Example 6
The difference between this example and example 1 is that the pre-doping element in the tricobalt tetraoxide is Mn.
Example 7
The present embodiment differs from embodiment 1 only in that in step (1), Y 2 O 3 The addition amount of Y is 100 mg/kg of the weight of the lithium cobalt oxide positive electrode material.
Example 8
The difference between this example and example 1 is that Ti was added in the amount of 2000 mg/kg by weight of the lithium cobalt oxide positive electrode material in the step (1).
Example 9
The difference between this example and example 1 is that in step (1), the amount of Mg added was 200 Mg/kg by weight of the lithium cobalt oxide positive electrode material.
Example 10
This example differs from example 1 only in that in step (3), co (OH) 2 The addition amount of (C) is 5000mg/kg of the weight of the primary sintered product.
Example 11
This example differs from example 1 only in that in step (1), tiO 2 The Ti in the alloy is 3000mg/kg of the weight of the primary sintered product.
Example 12
The present embodiment differs from embodiment 1 only in that, in step (3), al 2 O 3 Al in (C) is 3000mg/kg of the weight of the primary sintered product.
Example 13
The difference between this example and example 2 is only that in step (5), YF 3 F in (2) is 3000mg/kg of the weight of the primary sintered product.
Example 14
This example differs from example 2 only in that in step (5), LATP is 3000mg/kg of the weight of the primary sintered product.
Comparative example 1:
the preparation method of the lithium cobaltate cathode material of the present comparative example is substantially the same as in example 1, except that in step (1)The cobalt oxide is not a pre-doped raw material, the Al doping is changed into dry mixing during one-time batching, other operation steps are completely the same as those of the embodiment 1, and the specific process of the step (1) is as follows: (1) Particle diameter D 50 Is 3.5 mu m of cobaltosic oxide, lithium carbonate and Al 2 O 3 、Y 2 O 3 、TiO 2 And Mg (OH) 2 And (3) batching, and then mixing by adopting a coulter type mixer to obtain a primary mixture. Wherein the molar ratio of the lithium element in the lithium carbonate to the cobalt element in the cobaltosic oxide is n (Li): n (Co) =1.05:1, the addition amount of Al is 11000/Mg/kg of the weight of the lithium cobalt oxide positive electrode material, the addition amount of Y is 1000/Mg/kg of the weight of the lithium cobalt oxide positive electrode material, the addition amount of Ti is 500Mg/kg of the weight of the lithium cobalt oxide positive electrode material, and the addition amount of Mg is 1500Mg/kg of the weight of the lithium cobalt oxide positive electrode material.
Lithium cobaltate cathode material prepared in this comparative example, D thereof 0 2.23 μm, D 50 6.88 μm; specific surface area of 0.33 m 2 /g; the residual lithium content on the surface is 21mg/kg; a compacted density of 3.75g/cm 3 . The full battery assembled by the material is tested to have a discharge capacity of 179.8 mAh/g at 0.2C and a rate capability of 94.2% at 20C/0.2C in a voltage test range of 25 ℃ and 3.0V-4.45V; pulse discharge cycle 600 weeks capacity retention rate at 45 deg.c, 4C charge, 5A pulse discharge condition is 75.1%;85 DEG C&The thickness expansion rate at 4 hours was 9.1% and the capacity recovery rate was 92.2%. The physical properties and electrochemical properties of the positive electrode material products of this comparative example and example 1 are shown in tables 1 and 2.
Table 1 comparison of physical Properties of the cathode material products of comparative example 1 and example 1
Table 2 comparison of electrochemical properties of the cathode material products of comparative example 1 and example 1
As can be seen from the results of Table 2, the product obtained in example 1 has significantly improved capacity at high voltage, rate capability, high temperature cycle performance and high temperature storage performance, as compared with the lithium cobaltate cathode material prepared in comparative example 1. The method is mainly characterized in that the high-voltage and high-temperature performance requirements of the synthesized product are relatively high, so that the doping amount of Al is large, and if a wet pre-doping mode in tricobalt tetraoxide is not adopted, but dry mixing is adopted during one-time batching, the problems of uneven distribution of pre-doping element Al in the sintered product and segregation on a microscopic scale are necessarily caused. In the embodiment 1, cobaltosic oxide containing the pre-doped element Al is used as an important raw material, the cobalt element and the pre-doped element Al can be uniformly mixed at an atomic level in an intermediate product, and finally, the pre-doped element Al is completely and uniformly distributed on a microscopic scale in a synthesized high-voltage lithium cobaltate product, so that the product performance is improved.
Comparative example 2:
the preparation method of the lithium cobaltate cathode material of the comparative example is basically the same as that of the example 1, except that the pre-doping of the tricobalt tetraoxide in the step (1) is 5000 mg/kg of the weight of the lithium cobaltate cathode material, other operation steps are completely the same as that of the example 1, and the specific process of the step (1) is as follows: (1) Particle diameter D 50 3.5 mu m pre-doped cobaltosic oxide, lithium carbonate and Y 2 O 3 、TiO 2 And Mg (OH) 2 And (3) batching, and then mixing by adopting a coulter type mixer to obtain a primary mixture. The molar ratio of the lithium element in the lithium carbonate to the cobalt element in the cobaltosic oxide is n (Li): n (Co) =1.05:1, the pre-doping element Al in the cobaltosic oxide is 5000 Mg/kg of the weight of the lithium cobalt oxide positive electrode material, the adding amount of Y is 1000 Mg/kg of the weight of the lithium cobalt oxide positive electrode material, the adding amount of Ti is 500Mg/kg of the weight of the lithium cobalt oxide positive electrode material, and the adding amount of Mg is 1500Mg/kg of the weight of the lithium cobalt oxide positive electrode material.
Lithium cobaltate cathode material prepared in this comparative example, D thereof 0 2.27 μm, D 50 6.98 μm; specific surface area of 0.33 m 2 /g; the residual lithium content on the surface is 21mg/kg; a compacted density of 3.75g/cm 3 . The full battery assembled by the material is tested to have a discharge capacity of 182.4 mAh/g at 0.2C and a rate capability of 97 at 20C/0.2C in a voltage test range of 25 ℃ and 3.0V-4.45V. 5%; pulse discharge cycle 600 weeks capacity retention rate at 45 deg.c, 4C charge, 5A pulse discharge condition is 73.5%;85 DEG C&The thickness expansion ratio at 4 hours was 9.9% and the capacity recovery ratio was 91.1%. The physical properties and electrochemical properties of the positive electrode material products of this comparative example and example 1 are shown in tables 3 and 4.
TABLE 3 comparison of physical Properties of the cathode material products of comparative example 2 and example 1
Table 4 comparison of electrochemical properties of the cathode material products of comparative example 2 and example 1
As can be seen from the results of table 4, the product obtained in example 1, although the capacity and rate performance at high voltage were slightly lower, the high temperature cycle performance and the high temperature storage performance were significantly improved, compared with the lithium cobaltate cathode material prepared in comparative example 2; and the lithium cobaltate anode material prepared in comparative example 2 has high-temperature cycle performance and high-temperature storage performance which can not meet the performance requirements of the product protected by the invention (45 ℃ C. Pulse-discharge cycle 600 weeks is more than or equal to 80 percent; 85℃)&The thickness expansion rate is less than or equal to 8% and the capacity recovery rate is more than or equal to 94.0% in 4 hours). This is mainly because in the present invention M is present under high voltage and high temperature conditions 1 The additive mainly has the functions of stabilizing the structure, improving the thermal stability of the anode material and increasing the charge-discharge window; in addition, the high voltage and high temperature performance requirements of the product synthesized by the invention are relatively high, so M 1 The pre-doping amount of (c) cannot be too low.
Comparative example 3:
the preparation method of the lithium cobaltate cathode material of the comparative example is basically the same as that of the example 1, except that in the pre-doping of the cobaltosic oxide in the step (1), al is 16000 mg/kg of the weight of the lithium cobaltate cathode material, other operation steps are completely the same as that of the example 1, and the specific process of the step (1) is as follows: (1) Particle diameter D 50 3.5 mu m pre-doped cobaltosic oxide, lithium carbonate and Y 2 O 3 、TiO 2 And Mg (OH) 2 And (3) batching, and then mixing by adopting a coulter type mixer to obtain a primary mixture. The molar ratio of the lithium element in the lithium carbonate to the cobalt element in the cobaltosic oxide is n (Li): n (Co) =1.05:1, the pre-doping element Al in the cobaltosic oxide is 16000/Mg/kg of the weight of the lithium cobalt oxide positive electrode material, the addition amount of Y is 1000/Mg/kg of the weight of the lithium cobalt oxide positive electrode material, the addition amount of Ti is 500Mg/kg of the weight of the lithium cobalt oxide positive electrode material, and the addition amount of Mg is 1500Mg/kg of the weight of the lithium cobalt oxide positive electrode material.
Lithium cobaltate cathode material prepared in this comparative example, D thereof 0 2.19 μm, D 50 6.82 μm; specific surface area of 0.34 m 2 /g; the residual lithium content on the surface is 22mg/kg; a compacted density of 3.75g/cm 3 . The full battery assembled by the material is tested to have a 0.2C discharge capacity of 178.2 mAh/g and a 20C/0.2C rate performance of 93.1% in a voltage test range of 25 ℃ and 3.0V-4.45V; pulse discharge cycle 600 weeks capacity retention rate at 45 deg.c, 4C charge, 5A pulse discharge condition is 82.5%;85 DEG C &The thickness expansion rate at 4 hours was 6.2%, and the capacity recovery rate was 96.1%. The physical properties and electrochemical properties of the positive electrode material products of this comparative example and example 1 are shown in tables 5 and 6.
TABLE 5 comparison of physical Properties of the cathode material products of comparative example 3 and example 1
Table 6 comparison of electrochemical properties of the cathode material products of comparative example 3 and example 1
As can be seen from the results of table 6, the product obtained in example 1, although the high temperature cycle performance and the high temperature storage performance were slightly lower, the capacity and the rate performance at high voltage were remarkably improved, compared with the lithium cobaltate cathode material prepared in comparative example 3; and the capacity and rate capability of the lithium cobalt oxide positive electrode material prepared in comparative example 3 at high voltage are not satisfactory to the production of the present inventionThe performance requirement of the product (the discharge capacity of 0.2C is more than or equal to 180 mAh/g, and the rate capability of 20C/0.2C is more than or equal to 95.0%). This is mainly because M in the present invention 1 The additive mainly has the functions of stabilizing the structure, improving the thermal stability of the anode material and increasing the charge-discharge window; but M is 1 Too high a pre-doping amount tends to affect the capacity and rate capability of the material, so M 1 The pre-doping amount of (2) cannot be too high.
Comparative example 4:
the preparation method of the lithium cobaltate cathode material of the comparative example is basically the same as that of example 1, except that M is not added in step (1) 2 Doping element (M in example 1) 2 The element is Y), and other operation steps are exactly the same as those of the embodiment 1, and the specific process of the step (1) is as follows: (1) Particle diameter D 50 3.5 mu m pre-doped cobaltosic oxide, lithium carbonate and TiO 2 And Mg (OH) 2 And (3) batching, and then mixing by adopting a coulter type mixer to obtain a primary mixture. The molar ratio of the lithium element in the lithium carbonate to the cobalt element in the cobaltosic oxide is n (Li): n (Co) =1.05:1, the pre-doping element Al in the cobaltosic oxide is 11000/Mg/kg of the weight of the lithium cobalt oxide positive electrode material, the adding amount of Ti is 500/Mg/kg of the weight of the lithium cobalt oxide positive electrode material, and the adding amount of Mg is 1500Mg/kg of the weight of the lithium cobalt oxide positive electrode material.
Lithium cobaltate cathode material prepared in this comparative example, D thereof 0 2.11 μm, D 50 6.89 μm; specific surface area of 0.32 m 2 /g; the residual lithium content on the surface is 22mg/kg; a compacted density of 3.75g/cm 3 . The material is tested to have a discharge capacity of 178.4 mAh/g at 0.2C and a rate capability of 93.5% at 20C/0.2C in a full battery 25 ℃ and 3.0V-4.45V voltage test range; pulse discharge cycle 600 weeks capacity retention rate at 45 deg.c, 4C charge, 5A pulse discharge condition is 78.3%;85 DEG C&The thickness expansion rate at 4 hours was 8.5% and the capacity recovery rate was 92.7%. The physical properties and electrochemical properties of the positive electrode material products of this comparative example and example 1 are shown in tables 7 and 8.
TABLE 7 comparison of physical Properties of the cathode material products of comparative example 4 and example 1
Table 8 comparison of electrochemical properties of comparative example 4 and example 1 cathode material products
As can be seen from the results of table 8, the lithium cobaltate cathode material prepared in comparative example 4 without adding doping element Y has significantly improved capacity and rate performance at high voltage and also significantly improved high temperature cycle performance and high temperature storage performance compared with the product obtained in example 1. This shows that the invention selects the element Y with large ion radius, which is added during one sintering, on one hand, most of the element with large ion radius is doped to replace Co 3+ Part of the lithium ion battery forms a large-aperture ion channel, promotes lithium ion conduction, and remarkably improves the charge rate performance and discharge capacity of the lithium battery; on the other hand, a small amount of an element having a large ion radius does not enter the crystal lattice of lithium cobaltate, but forms a surface coating layer. The element Y is added during primary sintering, so that the effect of doping and surface coating is achieved, the element Y and other coating substances added during secondary sintering are combined to achieve the effect of double protection on lithium cobaltate, and the effects of improving capacity and multiplying power performance, high-temperature cycle performance and high-temperature storage performance are achieved.
Comparative example 5:
the preparation method of the lithium cobaltate cathode material of this comparative example is substantially the same as in example 1, except that in the step (5)
The nano-sized fast ion conductor is not added as a coating (the nano-sized fast ion conductor coating is LLZO in the embodiment 1), other operation steps are exactly the same as the embodiment 1, and the specific process of the step (5) is as follows: and (3) mixing the twice-burned crushed classified material obtained in the step (4) with the coating 2, and then carrying out high-speed mixing to obtain a three-time mixture. The coating 2 is LiF, wherein F in LiF is 1000 mg/kg of the weight of the primary sintered product.
Lithium cobaltate cathode material prepared in this comparative example, D thereof 0 2.15 μm, D 50 6.81 μm; specific surface area of 0.32 m 2 /g; the residual lithium content on the surface is 22mg/kg; a compacted density of 3.75g/cm 3 . The material is tested to have a discharge capacity of 178.9 mAh/g at 0.2C and a rate capability of 93.8% at 20C/0.2C in a full battery 25 ℃ and 3.0V-4.45V voltage test range; pulse discharge cycle 600 weeks capacity retention rate at 45 deg.c, 4C charge, 5A pulse discharge condition is 78.1%;85 DEG C&The thickness expansion ratio at 4 hours was 8.3%, and the capacity recovery ratio was 93.2%. The physical properties and electrochemical properties of the positive electrode material products of this comparative example and example 1 are shown in tables 9 and 10.
Table 9 comparison of physical Properties of the cathode material products of comparative example 5 and example 1
Table 10 comparison of electrochemical properties of comparative example 5 and example 1 cathode material products
As can be seen from the results of Table 10, the product obtained in example 1 has certain advantages in terms of capacity at high voltage, rate capability, high temperature cycle performance and high temperature storage performance, as compared with the product of comparative example 5. The invention is characterized in that the nano fast ion conductor is coated on the surface of the lithium cobalt oxide anode material, on one hand, the nano fast ion conductor coating layer is used as a protective layer to isolate the electrolyte from directly contacting with the anode material, thereby reducing related side reactions, such as cobalt dissolution, forming thinner SEI film and the like, and improving the electrochemical stability of the material; on the other hand, the nano fast ion conductor coating layer has high ion conductivity and excellent thermal stability, can obviously improve the conductivity of the material, reduce the internal resistance and realize the fast charge and discharge and high-temperature cycle performance of the lithium ion battery.
Comparative example 6:
the preparation method of the lithium cobaltate cathode material of the comparative example is basically the same as that of the example 1, except that fluoride is not added as a coating in the step (5) (the fluoride coating is LiF in the example 1), other operation steps are exactly the same as that of the example 1, and the specific process of the step (5) is as follows: and (3) mixing the twice-burned crushed classified material obtained in the step (4) with the coating 2, and then carrying out high-speed mixing to obtain a three-time mixture. The coating 2 was LLZO, wherein LLZO was 1000 mg/kg of the weight of the primary sintered product.
Lithium cobaltate cathode material prepared in this comparative example, D thereof 0 2.18 μm, D 50 6.85 μm; specific surface area of 0.32 m 2 /g; the residual lithium content on the surface is 20mg/kg; a compacted density of 3.75g/cm 3 . The material is tested to have a discharge capacity of 182.2 mAh/g at 0.2C and a rate capability of 97.2% at 20C/0.2C in a full battery 25 ℃ and 3.0V-4.45V voltage test range; pulse discharge cycle 600 weeks capacity retention rate at 45 deg.c, 4C charge, 5A pulse discharge condition is 77.2%;85 DEG C&The thickness expansion rate at 4 hours was 9.1% and the capacity recovery rate was 93.0%. The physical properties and electrochemical properties of the positive electrode material products of this comparative example and example 1 are shown in tables 11 and 12.
Table 11 comparison of physical Properties of the cathode material products of comparative example 6 and example 1
Table 12 comparison of electrochemical properties of the cathode material products of comparative example 6 and example 1
As can be seen from the results of Table 12, it was found that the product obtained in example 1 has certain advantages in both high temperature cycle performance and high temperature storage performance at high voltage, as compared with the product of comparative example 6. The invention is characterized in that fluoride is coated on the surface of the lithium cobalt oxide positive electrode material, and the fluoride is coated and modified by the fluoride, so that the cycle and high-temperature storage performance under high voltage are obviously improved, and the irreversible phase change and gas production are effectively inhibited.
Comparative example 7:
the preparation method of the lithium cobalt oxide positive electrode material of this comparative example was the same as in step (1) and step (2) of example 1, except that two sintering was used in this comparative example. The procedure for the preparation of comparative example 7 is as follows:
(1) Particle diameter D 50 3.5 mu m pre-doped cobaltosic oxide, lithium carbonate and Y 2 O 3 、TiO 2 And Mg (OH) 2 And (3) batching, and then mixing by adopting a coulter type mixer to obtain a primary mixture. The molar ratio of the lithium element in the lithium carbonate to the cobalt element in the cobaltosic oxide is n (Li): n (Co) =1.05:1, the pre-doping element Al in the cobaltosic oxide is 11000 Mg/kg of the weight of the lithium cobalt oxide positive electrode material, the adding amount of Y is 1000 Mg/kg of the weight of the lithium cobalt oxide positive electrode material, the adding amount of Ti is 500Mg/kg of the weight of the lithium cobalt oxide positive electrode material, and the adding amount of Mg is 1500Mg/kg of the weight of the lithium cobalt oxide positive electrode material.
(2) Placing the uniformly mixed primary mixture obtained in the step (1) in an atmosphere with the oxygen mass fraction of 23% and the ventilation of 25m 3 And under the condition of/h, the temperature is raised to 750 ℃ from room temperature, the temperature is kept for 4 hours, then the temperature is raised to 1050 ℃, the temperature is kept for 10 hours, and the materials are naturally cooled along with the furnace. Coarse crushing the material after primary sintering by a jaw crusher and a twin-roll mill, and crushing and grading by an environment-friendly fluidized bed type totally-enclosed supersonic jet crushing integrated machine to obtain a primary-sintering crushed graded material. Particle size D of one-time baking crushed graded material 0 1.2 μm, D 50 5.4 μm. The parameters for comminution and classification are as follows: the grinding air pressure is 0.6 MPa, the frequency of a grading motor is 24Hz, the frequency of a feeding motor is 9Hz, and the pressure of a grinding body is-1.5 KPa.
(3) And (3) proportioning the primary-burned crushed classified material obtained in the step (2) and the coating according to a certain proportion, and then mixing by adopting a high-speed mixer to obtain a secondary mixture. The coating is Co (OH) 2 、TiO 2 、Al 2 O 3 Combinations of LLZO, liF. Wherein Co (OH) 2 15000 mg/kg of the weight of the primary sintered product; tiO (titanium dioxide) 2 Ti in the alloy is 500 mg/kg of the weight of the primary sintered product; al (Al) 2 O 3 Al in the alloy is 900 mg/kg of the weight of the primary sintered product; LLZO is 1000 weight of primary sintered productmg/kg; f in LiF is 1000 mg/kg of the weight of the primary sintered product.
(4) The obtained secondary mixture was placed in an atmosphere having an oxygen mass fraction of 23% and a ventilation of 15m 3 And under the condition of/h, heating from room temperature to 950 ℃, preserving heat for 10 hours, then cooling to 820 ℃, preserving heat for 3 hours, and then naturally cooling along with a furnace. Coarse crushing the material after secondary sintering by a jaw crusher and a pair roller, crushing and grading by an environment-friendly fluidized bed type totally-enclosed supersonic jet crushing integrated machine to obtain a secondary-sintering crushed graded material, and then performing demagnetizing and sieving to obtain the high-temperature-rate lithium cobalt oxide anode material. Particle size D of the secondary combustion crushed graded material 0 2.20 μm, D 50 6.80 μm. The parameters for the comminution and classification are as follows: the grinding air pressure is 0.38MPa, the frequency of a grading motor is 28Hz, the frequency of a feeding motor is 10Hz, and the pressure of a grinding body is-4.7 KPa.
Lithium cobaltate cathode material prepared in this comparative example, D thereof 0 2.20 μm, D 50 6.80 μm; specific surface area of 0.31 and 0.31 m 2 /g; the residual lithium content on the surface is 25mg/kg; a compacted density of 3.75g/cm 3 . The material is tested to have a discharge capacity of 180.1 mAh/g at 0.2C and a rate capability of 95.2% at 20C/0.2C in a full battery 25 ℃ and 3.0V-4.45V voltage test range; pulse discharge cycle 600 weeks capacity retention rate at 45 deg.c, 4C charge, 5A pulse discharge condition is 75.1%;85 DEG C&The thickness expansion ratio at 4 hours was 12.3%, and the capacity recovery ratio was 91.2%. The physical properties and electrochemical properties of the positive electrode material products of this comparative example and example 1 are shown in tables 13 and 14.
TABLE 13 comparison of physical Properties of the cathode Material products of comparative example 7 and example 1
Table 14 comparison of electrochemical properties of comparative example 7 and example 1 cathode material products
From the results of Table 14, it is possible toIt is seen that since comparative example 7 was not separately clad according to the characteristics of the clad, five clad Co (OH) were formed at the time of secondary sintering 2 、TiO 2 、Al 2 O 3 The LLZO and LiF are coated together, and the ideal coating effect is not achieved, so that the electrochemical performances including capacity, multiplying power, high-temperature cycle, high-temperature storage and the like are poorer than those of the embodiment 1.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the high-temperature high-rate lithium cobalt oxide positive electrode material is characterized by comprising the following steps of:
(1) Will be pre-doped with element M 1 Cobalt source, lithium source, M-containing 2 Compounds of (C) containing M 3 Compounds of (2) and M-containing compounds 4 The compound of (2) is mixed to obtain a primary mixture; m is M 1 One or more selected from Al, ni and Mn; m is M 2 One or more than two selected from La, gd and Y; m is M 3 One or more than two of Ti, nb and V; m is M 4 One or more than two of B, mg and Li;
(2) Performing first sintering on the primary mixture, and then crushing and grading to obtain a first-sintering crushed graded material;
(3) The first-fired crushed classified material and the first coating are mixed to obtain a secondary mixture; the first coating is selected from one or more than two of cobalt-containing compounds, titanium-containing compounds and aluminum-containing compounds;
(4) Performing secondary sintering on the secondary mixture, and then crushing and grading to obtain a secondary-sintering crushed graded material;
(5) Mixing the secondary-burning crushed classified material with a second coating material to obtain a tertiary mixture; the second coating is a mixture of a nano fast ion conductor and fluoride;
(6) And (3) carrying out third sintering on the tertiary mixture, and carrying out dissociation, demagnetization and sieving to obtain the high-temperature high-magnification lithium cobalt oxide anode material.
2. The method for preparing a high-temperature high-rate lithium cobalt oxide positive electrode material according to claim 1, wherein the M is 1 The doping amount of the lithium cobalt oxide anode material is 6000-15000 mg/kg of the weight of the lithium cobalt oxide anode material;
containing M 2 Is selected from one or more of hydroxide, hydroxyl oxide, carbonic acid compound and acetic acid compound in La, gd and Y; the M is 2 The doping amount of the lithium cobalt oxide anode material is 100-2000 mg/kg;
containing M 3 The compound is one or more than two of hydroxide, hydroxyl oxide, carbonic acid compound and acetic acid compound in Ti, nb and V; the M is 3 The doping amount of the lithium cobalt oxide anode material is 100-2000 mg/kg of the weight of the lithium cobalt oxide anode material;
Containing M 4 The compound is one or more than two of hydroxide, hydroxyl oxide, carbonic acid compound and acetic acid compound in B, mg and Li; containing M 4 The addition amount of the compound is 100-2000 mg/kg of the weight of the lithium cobalt oxide anode material;
the cobalt source is selected from one or more of cobalt hydroxide, cobaltous hydroxide, cobaltosic oxide, cobalt nitrate, cobalt carbonate, cobalt chloride, cobalt phosphate, cobalt acetylacetonate and cobalt sulfate;
the molar ratio of the lithium element of the lithium source to the cobalt element of the cobalt source, n (Li): n (Co), is 1.1-1.0:1.
3. The method for preparing a high-temperature high-rate lithium cobalt oxide positive electrode material according to claim 1, wherein in the step (2), the first sintering comprises: oxygen mass fraction in sintering atmosphere is 20% -100%, ventilation is 21-30 m 3 Heating the primary mixture to 720-780 ℃ under the condition of/h, preserving heat for 2-6 hours, then heating to 950-1200 ℃ and preserving heat for 8-12 hoursWhen (1).
4. The method for producing a high-temperature high-rate lithium cobalt oxide positive electrode material according to claim 1, wherein in the step (3), the cobalt-containing compound is selected from the group consisting of Co (OH) 2 One or more of cobalt oxyhydroxide, cobaltous hydroxide and cobaltosic oxide; the cobalt-containing compound is 5000-40000 mg/kg of the weight of the primary sintering material;
The titanium-containing compound is selected from TiO 2 One or two of titanium hydroxide; ti in the titanium-containing compound is 100-3000 mg/kg of the weight of the primary sintering material;
the aluminum-containing compound is selected from Al 2 O 3 One or two of aluminum hydroxide; al in the aluminum-containing compound is 200-3000 mg/kg of the weight of the primary sintering material;
the nanometer fast ion conductor is selected from one or more than two of nanometer Lithium Aluminum Titanium Phosphate (LATP), nanometer Lithium Lanthanum Zirconium Oxide (LLZO) and nanometer Lithium Lanthanum Titanate (LLTO); the weight of the nano fast ion conductor is 200-3000 mg/kg of the weight of the primary sintering material;
the fluoride is selected from LiF and AlF 3 、YF 3 、TiF 4 One or two or more of them; f in the fluoride is 200-3000 mg/kg of the weight of the primary sintering material.
5. The method for preparing a high-temperature high-rate lithium cobalt oxide positive electrode material according to claim 1, wherein in the step (4), the second sintering comprises: the oxygen mass fraction in the sintering atmosphere is 20-100%, and the ventilation is 10-20 m 3 And (3) under the condition of/h, the secondary mixture is kept at 900-980 ℃ for 8-12 hours, and then kept at 800-850 ℃ for 2-4 hours.
6. The method for preparing a high-temperature high-rate lithium cobalt oxide positive electrode material according to claim 2, wherein the third sintering comprises: the oxygen mass fraction in the sintering atmosphere is 20-100%, and the ventilation is 10-20 m 3 Under the condition of/h, heat preservation is carried out for 8 to 12 hours at 770 to 870 DEG CWhen (1).
7. The method for preparing a high-temperature high-rate lithium cobalt oxide positive electrode material according to claim 2, wherein the particle size of the one-firing crushed graded material is as follows: d (D) 0 ≥ 0.5μm，D 50 4.5-7.5 mu m;
the particle size requirements of the secondary combustion crushing and grading material are as follows: d (D) 0 ≥ 0.5μm，D 50 6.0-9.0 mu m;
in the step (2) or the step (4), the pulverizing and classifying includes: firstly, adopting a jaw crusher and a twin-roll mill for coarse crushing, and then adopting an environment-friendly fluidized bed type totally-enclosed supersonic jet crushing integrated machine for crushing and grading.
8. The method for preparing a high-temperature high-rate lithium cobalt oxide positive electrode material according to claim 7, wherein in the step (2), the parameters for crushing and classifying by using an environment-friendly fluidized bed type totally-enclosed supersonic jet crushing integrated machine are as follows: the grinding air pressure is 0.56-0.65 MPa, the frequency of a grading motor is 15-33 Hz, the frequency of a feeding motor is 7-11 Hz, and the grinding body pressure is-0.9 to-2.0 KPa;
in the step (4), the parameters of crushing and classifying by adopting the environment-friendly fluidized bed type totally-enclosed supersonic jet crushing integrated machine are as follows: the grinding air pressure is 0.35-0.41 MPa, the grading motor frequency is 25-31 Hz, the feeding motor frequency is 6-14 Hz, and the grinding body pressure is-4.0 to-5.4 KPa.
9. The high-temperature rate lithium cobalt oxide positive electrode material prepared by the preparation method according to any one of claims 1 to 8, wherein the positive electrode material has D 0 ≥0.5μm，D 50 6.0-9.0 mu m; specific surface area of 0.15-0.45 m 2 /g; the residual lithium on the surface is 10-40 mg/kg; the compaction density is 3.7-3.9 g/cm 3 。
10. The high-temperature rate lithium cobalt oxide positive electrode material according to claim 9, wherein the discharge capacity of the full battery assembled by the positive electrode material is more than or equal to 180 mAh/g at 0.2C in a voltage test range of 3.0V-4.45V at 25 ℃, and the ratio of the discharge capacity under 0.2C charge and 20C discharge conditions to the discharge capacity under 0.2C charge and discharge conditions is not lower than 95.0%; 4C/5A pulse-free circulation at 45 ℃ for 600 weeks is more than or equal to 80%; the thickness expansion rate is less than or equal to 8% at 85 ℃ and less than 4 hours, and the capacity recovery rate is more than or equal to 94.0%.
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