CN109119621B - Lithium lanthanum titanate-lithium titanate coated nickel cobalt lithium aluminate anode material and preparation method thereof - Google Patents
Lithium lanthanum titanate-lithium titanate coated nickel cobalt lithium aluminate anode material and preparation method thereof Download PDFInfo
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- CN109119621B CN109119621B CN201811057336.6A CN201811057336A CN109119621B CN 109119621 B CN109119621 B CN 109119621B CN 201811057336 A CN201811057336 A CN 201811057336A CN 109119621 B CN109119621 B CN 109119621B
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- titanate
- lanthanum
- nickel cobalt
- aluminate
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 98
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 75
- RJEIKIOYHOOKDL-UHFFFAOYSA-N [Li].[La] Chemical compound [Li].[La] RJEIKIOYHOOKDL-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000010405 anode material Substances 0.000 title claims description 23
- 239000010936 titanium Substances 0.000 claims abstract description 38
- 238000003756 stirring Methods 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 34
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 33
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 22
- 239000010406 cathode material Substances 0.000 claims abstract description 21
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 17
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- 239000000725 suspension Substances 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 21
- 239000011247 coating layer Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 10
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 8
- IWTZGPIJFJBSBX-UHFFFAOYSA-G aluminum;cobalt(2+);nickel(2+);heptahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Co+2].[Ni+2] IWTZGPIJFJBSBX-UHFFFAOYSA-G 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical group [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 2
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 claims 1
- 229910000659 lithium lanthanum titanates (LLT) Inorganic materials 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000007774 positive electrode material Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000011163 secondary particle Substances 0.000 description 7
- 230000001351 cycling effect Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000013543 active substance Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 229910015639 LiNi0.815Co0.15Al0.035O2 Inorganic materials 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 2
- -1 Lithium nickel cobalt aluminates Chemical class 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 2
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910019421 CoxAly Inorganic materials 0.000 description 1
- 229910016194 LiNi0.9Co0.07Al0.03O2 Inorganic materials 0.000 description 1
- 229910012672 LiTiO Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- AWDNMRMONHVGOI-UHFFFAOYSA-N [Ni].[Li].[La] Chemical compound [Ni].[Li].[La] AWDNMRMONHVGOI-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- 231100000719 pollutant Toxicity 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- 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
本发明涉及一种钛酸镧锂‑钛酸锂包覆的镍钴铝酸锂正极材料及其制备方法。所述制备方法包括如下步骤：S1：将有机钛源和镧源溶于有机溶剂，搅拌得混合溶液；S2：向混合溶液中加入镍钴铝酸锂和表面活性剂，于60~80℃搅拌得悬浮液；S3：在搅拌条件下逐滴加入水，继续搅拌至有机溶剂挥发完全，烘干得包覆材料；S4：将包覆材料于450~650℃条件下煅烧5~10 h即得到钛酸镧锂‑钛酸锂包覆的镍钴铝酸锂正极材料。本发明提供的制备方法操作简单、易于工业化，适于在本领域内推广使用；制备得到的钛酸锂‑钛酸镧锂包覆的镍钴铝酸锂正极材料具有优异的电化学性能和循环稳定性。
The invention relates to a lithium lanthanum titanate-lithium titanate-coated nickel cobalt lithium aluminate cathode material and a preparation method thereof. The preparation method includes the following steps: S1: dissolving an organic titanium source and a lanthanum source in an organic solvent, and stirring to obtain a mixed solution; S2: adding nickel cobalt lithium aluminate and a surfactant to the mixed solution, and stirring at 60-80° C. to obtain a suspension; S3: add water dropwise under stirring conditions, continue stirring until the organic solvent is completely volatilized, and dry to obtain a coating material; S4: calcine the coating material at 450-650 °C for 5-10 h to obtain Lithium lanthanum titanate-lithium titanate-coated nickel cobalt lithium aluminate cathode material. The preparation method provided by the invention is simple to operate, easy to industrialize, and suitable for popularization and use in the field; the prepared lithium titanate-lithium lanthanum titanate-coated nickel cobalt lithium aluminate cathode material has excellent electrochemical performance and cycle stability.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a lithium lanthanum titanate-lithium titanate-coated nickel cobalt lithium aluminate anode material and a preparation method thereof.
Background
In recent years, due to the large amount of exploitation of natural resources, non-renewable energy sources such as petroleum, natural gas and coal with limited reserves gradually tend to be exhausted; on the other hand, the great emission of automobile exhaust and factory pollutants also makes people's living environment change greatly. Compelling these two pressures, people are gradually turning their eyes to cleaner and more efficient renewable resourcesEnergy sources, such as: solar, wind, tidal, etc. And the lithium ion battery is used as an energy storage medium, and can effectively store the energy. Therefore, the development of an energy storage device with excellent overall performance is the key to the solution. In lithium ion batteries, positive electrode materials have been considered as a core part thereof for cost and technical considerations. And high nickel ternary material (LiNi)1-xMO2(ii) a M ═ Co, Mn, Al; x ≦ 0.4) has been widely noted and studied because of its higher specific capacity and acceptable cost. With lithium nickel cobalt aluminate (LiNi)1-x-yCoxAlyO2；x+y≤0.2，0<x<1，0<y<1) The specific capacity of the cathode material can reach 185mAh/g, but the unstable surface chemistry and the inherent structural instability of the cathode material provide great challenges for the industrial application of the cathode material. A certain amount of residual lithium often exists on the surface of the material, and the residual lithium is usually in the form of lithium hydroxide, lithium carbonate, lithium oxide and the like, so that the high alkalinity and high water absorption of the material are caused, which not only causes difficulty for the subsequent coating process of the material, but also puts higher requirements on the alkali resistance of the electrolyte. In addition, in the charged state, Ni, which is highly active on the particle surface4+It is highly susceptible to side reactions with the electrolyte and increases the impedance and reversible capacity loss of the battery. Therefore, during repeated charge and discharge processes, such deterioration phenomenon may further diffuse from the surface to the inside, thereby deteriorating the electrochemical performance of the entire battery. Therefore, the stable particle surface is of great significance to the ternary nickel material.
Therefore, strategies such as coating, doping and complex structural design are adopted to improve the rate capability and the cycle performance of the material, but the improvement effect is not ideal.
Therefore, how to improve the electrochemical performance, the capacity and the cycling stability of the nickel-cobalt lithium aluminate anode material is a research focus and a technical difficulty in the research field of the lithium ion battery at present, and the breakthrough of the technology is helpful for further improving the overall performance of the lithium ion battery.
Disclosure of Invention
The invention aims to overcome the defects and defects of unstable surface chemical property and internal structure of a nickel cobalt lithium aluminate anode material in the prior art, and provides a preparation method of a lanthanum lithium titanate-lithium titanate coated nickel cobalt lithium aluminate anode material. The preparation method provided by the invention utilizes residual lithium on the surface of secondary particles, adds titanium and lanthanum, and forms a uniform lanthanum lithium titanate-lithium titanate coating layer through high-temperature sintering, thereby obviously reducing the residual lithium amount and alkalinity on the surface of the material, effectively inhibiting the occurrence of side reaction between an active substance and electrolyte, and playing a role in stabilizing the surface chemical property of the material; in addition, the coating layer of the lanthanum lithium titanate-lithium titanate can simultaneously improve the ion conductivity and the electrical conductivity of the material at the interface, and finally improve the dynamic performance and the electrochemical performance of the material at the interface; the prepared lithium titanate-lanthanum lithium titanate coated nickel cobalt lithium aluminate cathode material has excellent electrochemical performance and cycling stability.
The invention also aims to provide a lithium lanthanum titanate-lithium titanate coated nickel cobalt lithium aluminate cathode material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a lithium lanthanum titanate-lithium titanate coated nickel cobalt lithium aluminate anode material comprises the following steps:
s1: dissolving an organic titanium source and a lanthanum source in an organic solvent, and stirring to obtain a mixed solution, wherein the molar ratio of lanthanum in the lanthanum source to titanium in the titanium source is 0.5-2: 1; the titanium source and the lanthanum source are uniformly mixed in the organic solvent to form a homogeneous solution, so that the subsequent treatment is convenient.
S2: adding nickel-cobalt lithium aluminate and a surfactant into the mixed solution, and stirring at 60-80 ℃ to obtain a suspension; the molar ratio of nickel, cobalt and aluminum in the nickel-cobalt lithium aluminate is 80-90: 7-15: 3-5; the molar ratio of the titanium source to the nickel cobalt lithium aluminate is 0.5-2: 100; under the action of the surfactant, the nickel-cobalt lithium aluminate can be uniformly dispersed and can interact with organic titanium, so that the titanium source is uniformly distributed around the nickel-cobalt lithium aluminate particles.
S3: dropwise adding water under the stirring condition, continuously stirring until the organic solvent is completely volatilized, and drying to obtain a coating material; slowly dripping deionized water to hydrolyze the uniformly distributed organic titanium source in the suspension, and preventing local agglomeration due to too fast hydrolysis rate.
S4: calcining the coated material at the temperature of 450-650 ℃ for 5-10 h to obtain the lithium lanthanum titanate-lithium titanate coated nickel cobalt lithium aluminate anode material. The titanium source and the lanthanum source are uniformly distributed on the surface of the nickel cobalt lithium aluminate particles, and react with residual lithium on the surface of the particles during high-temperature sintering to form a uniform coating layer of a lanthanum lithium titanate-lithium titanate heterostructure.
The method comprises the steps of firstly, adding titanium and lanthanum into residual lithium on the surface of secondary particles, and sintering at high temperature to form a uniform lanthanum lithium titanate-lithium titanate coating layer. The method not only reduces the residual lithium amount and alkalinity of the material, but also introduces a coating layer of a fast ion conductor on the surface of the material, thereby greatly accelerating the migration rate of lithium ions at the interface. In addition, the heterostructure coating layer of the lanthanum lithium titanate-lithium titanate can improve the spatial arrangement of electron cloud and remarkably improve the conductivity of the interface layer. Therefore, the coating layer of the lanthanum lithium titanate-lithium titanate can not only prevent the occurrence of side reaction between the active substance and the electrolyte, but also improve the ion conductivity and the electrical conductivity of the material at the interface, and finally improve the electrochemical performance of the material.
The modified nickel cobalt lithium aluminate anode material prepared by the preparation method of the lanthanum lithium titanate-lithium titanate coated nickel cobalt lithium aluminate anode material has the advantages that the particle size distribution is uniform, the secondary particle size is about 10 mu m, the primary particle size is about 500nm, the coating layer is uniformly distributed on the surface of the secondary particle size, and the thickness is about 4-10 nm. The button cell assembled by the prepared nickel cobalt lithium aluminate anode material is subjected to charge and discharge tests at 0.1 ℃, the first discharge gram specific capacity reaches more than 190mAh/g, and the first coulombic efficiency reaches 90.2%; the button cell assembled by the prepared nickel cobalt lithium aluminate anode material is subjected to charge and discharge tests at 1C, after 100 times of circulation, the discharge specific capacity retention rate is about 95%, and after 300 times of 5C circulation, the capacity retention rate is about 85%. Therefore, the lithium titanate-lanthanum lithium titanate coated nickel cobalt lithium aluminate cathode material has excellent electrochemical performance and cycling stability.
Organic titanium sources, lanthanum sources, and organic solvents conventional in the art may be used in the present invention.
Preferably, the organic titanium source in S1 is one or both of tetrabutyl titanate or tetraisopropyl titanate.
Preferably, the lanthanum source is one or both of lanthanum acetate or lanthanum nitrate.
Preferably, the organic solvent is one or more of ethanol, ethylene glycol or glycerol.
Preferably, the molar ratio of the lanthanum element in the lanthanum source and the titanium element in the titanium source in S1 is 1:1.
The lithium titanate-lanthanum lithium titanate coated nickel cobalt lithium aluminate anode material prepared under the condition of the specific dosage relation has more excellent electrochemical performance and cycling stability.
Surfactants conventional in the art may be used in the present invention.
Preferably, the surfactant in S2 is one or both of polyvinylpyrrolidone PVP or cetyltrimethylammonium bromide CTAB.
Preferably, the mass ratio of the surfactant to the lithium nickel cobalt aluminate in S2 is 0.5-2: 100.
Preferably, the molar ratio of nickel, cobalt and aluminium in the lithium nickel cobalt aluminate in S2 is 81.5:15: 3.5.
Preferably, the molar ratio of the titanium source to the lithium nickel cobalt aluminate in S2 is 1: 100.
Lithium nickel cobalt aluminates of the prior art are all useful in the present invention. The invention also provides a preparation method of the nickel cobalt lithium aluminate.
Preferably, the nickel cobalt lithium aluminate is prepared by the following method: dissolving a nickel source, a cobalt source and an aluminum source to obtain a mixed solution, adding ammonia water and an inorganic strong alkali solution to adjust the pH to 10.9-11.7, reacting, washing and drying to obtain a nickel-cobalt-aluminum hydroxide precursor; and then mixing and grinding the nickel-cobalt-aluminum hydroxide precursor and a lithium source, and calcining for 12-18 h at 720-780 ℃ in an oxygen atmosphere to obtain the nickel-cobalt-lithium aluminate.
The nickel-cobalt lithium aluminate material prepared by the method has high initial specific capacity, uniform size distribution and good sphericity, and is beneficial to subsequent processing.
Preferably, the nickel source is one or more of nickel sulfate, nickel nitrate or nickel acetate.
Preferably, the cobalt source is one or more of cobalt sulfate, cobalt nitrate or cobalt acetate.
Preferably, the total concentration of the metals in the mixed solution is 1-4 mol/L.
Preferably, the inorganic strong base is sodium hydroxide or potassium hydroxide.
Preferably, the concentration of the inorganic strong base is 2-8 mol/L; the concentration of the ammonia water is 2-4 mol/L.
Preferably, the lithium source is one or more of lithium hydroxide monohydrate, lithium carbonate or lithium acetate.
Preferably, the molar ratio of the nickel cobalt aluminum hydroxide precursor to the lithium source is 1: 01-1.10.
More preferably, the molar ratio of the nickel cobalt aluminum hydroxide precursor to the lithium source is 1: 1.05.
Preferably, the calcination temperature is 750 ℃ and the calcination time is 15 h.
Preferably, the molar ratio of the water to the titanium element in the titanium source in S3 is 2-4: 1.
Preferably, the calcination in S4 is carried out at a temperature of 650 ℃ for a period of 5 h.
The lithium lanthanum titanate-lithium titanate coated nickel cobalt lithium aluminate cathode material is prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, residual lithium on the surface of secondary particles is added with titanium and lanthanum, and a uniform lanthanum lithium titanate-lithium titanate coating layer is formed through high-temperature sintering, so that the residual lithium amount and alkalinity of the surface of the material are obviously reduced, the occurrence of side reactions between active substances and electrolyte is effectively inhibited, and the effect of stabilizing the surface chemical properties of the material is achieved; in addition, the coating layer of the lanthanum lithium titanate-lithium titanate can simultaneously improve the ion conductivity and the electrical conductivity of the material at the interface, and finally improve the dynamic performance and the electrochemical performance of the material at the interface; the prepared lithium titanate-lanthanum lithium titanate coated nickel cobalt lithium aluminate cathode material has excellent electrochemical performance and cycling stability. The preparation method provided by the invention is simple to operate, easy to industrialize and suitable for popularization and use in the field.
Drawings
Fig. 1 is an XRD spectrum of the lithium lanthanum titanate-lithium titanate coated lithium nickel cobalt aluminate positive electrode material prepared in example 1 of the present invention;
fig. 2 is a scanning electron microscope picture of the lithium lanthanum titanate-lithium titanate coated lithium nickel cobalt aluminate anode material prepared in example 1 of the present invention;
fig. 3 is a high power transmission microscope picture of the lithium lanthanum titanate-lithium titanate coated lithium nickel cobalt aluminate anode material prepared in example 1 of the present invention;
fig. 4 is a first charge-discharge curve of a button cell assembled from a lithium nickel cobalt aluminate positive electrode material coated with lanthanum lithium titanate and lithium titanate provided in embodiment 1 of the present invention, which is obtained by performing a charge-discharge test at a 0.1C rate using a shenzhen novei high performance battery test system;
fig. 5 is a krf capacity cycle curve of 100 cycles of charge and discharge of a button battery assembled from a lithium nickel cobalt aluminate positive electrode material coated with lanthanum lithium titanate and lithium titanate provided in embodiment 1 of the present invention, which is subjected to a charge and discharge test at a 1C rate using a shenzhen newway high performance battery test system;
fig. 6 is a krf capacity cycle curve of a button battery assembled from a lithium lanthanum titanate-lithium titanate-coated lithium nickel cobalt aluminate positive electrode material and subjected to a charge and discharge test at a 5C rate by using a shenzhen newway high performance battery test system, and the charge and discharge are cycled for 300 times, provided by embodiment 1 of the present invention.
Detailed Description
The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
Example 1
The embodiment provides a lithium lanthanum titanate-lithium titanate coated lithium nickel cobalt aluminate cathode material. Prepared by the following preparation method.
(1) Dissolving tetrabutyl titanate in a proper amount of ethanol solvent, fully stirring, and adding a certain amount of lanthanum nitrate to ensure that the ratio of Ti: la is 1:1, and then fully stirring is carried out until colorless transparent solution is formed;
(2) reacting LiNi0.815Co0.15Al0.035O2And 1 wt% (relative to the nickel cobalt lithium aluminate) of PVP (polyvinylpyrrolidone) are added into the solution and placed in a constant water bath at 80 ℃ to be fully stirred to form a uniform suspension, wherein the molar ratio of titanium to the nickel cobalt lithium aluminate is 1: 100;
(3) adding deionized water dropwise under stirring to slowly hydrolyze tetrabutyl titanate, wherein the molar ratio of the amount of the deionized water to the added titanium source is 2: 1. Fully stirring until the solvent is completely evaporated, and drying the obtained product in an oven at 100 ℃ for 16 hours;
(4) and calcining the obtained coating material at 650 ℃ for 5 hours to obtain the lithium lanthanum titanate-lithium titanate coated nickel cobalt lithium aluminate anode material.
The nickel cobalt lithium aluminate in the step (2) is prepared by the following method: preparing nickel sulfate, cobalt sulfate and aluminum sulfate into 2mol L according to the molar ratio of 81.5:15:3.5-1Solution, 4mol L-1Aqueous ammonia solution and 8mol L-1And simultaneously adding a sodium hydroxide solution into the reactor for coprecipitation reaction, adjusting the flow of the sodium hydroxide solution to ensure that the pH of the system is 11.0, and filtering, washing and drying the obtained precipitate after 12-hour reaction to obtain the nickel-cobalt-aluminum hydroxide precursor. Grinding the precursor and lithium hydroxide monohydrate according to a molar ratio of 1:1.05, and calcining at the high temperature of 750 ℃ for 15 hours in an oxygen atmosphere to obtain the nickel-cobalt lithium aluminate anode material LiNi0.815Co0.15Al0.035O2。
By adjusting the dosage of the nickel source, the cobalt source and the aluminum source, the nickel-cobalt lithium aluminate with different molar ratios of nickel, cobalt and aluminum can be obtained. The nickel cobalt lithium aluminates in the subsequent examples were all prepared by this method.
Example 2
The embodiment provides a lithium lanthanum titanate-lithium titanate coated lithium nickel cobalt aluminate cathode material. Prepared by the following preparation method.
(1) Dissolving tetraisopropyl titanate in a proper amount of glycol solvent, fully stirring, and adding a certain amount of lanthanum acetate to ensure that the molar ratio of Ti: la is 1:2, and then fully stirring is carried out until colorless transparent solution is formed;
(2) reacting LiNi0.9Co0.07Al0.03O2And 0.5 wt% (relative to the lithium nickel cobalt aluminate) of CTAB (cetyltrimethylammonium bromide) were added to the above solution and placed in a constant water bath at 80 ℃ with thorough stirring to form a homogeneous suspension, wherein the molar ratio of titanium to lithium nickel cobalt aluminate was 0.5: 100;
(3) adding deionized water dropwise under stirring to slowly hydrolyze tetrabutyl titanate, wherein the molar ratio of the amount of the deionized water to the added titanium source is 4: 1. Fully stirring until the solvent is completely evaporated, and drying the obtained product in an oven at 120 ℃ for 12 hours;
(4) and calcining the obtained coating material at 450 ℃ for 10h to obtain the lithium lanthanum titanate-lithium titanate coated nickel cobalt lithium aluminate anode material.
Example 3
The embodiment provides a lithium lanthanum titanate-lithium titanate coated lithium nickel cobalt aluminate cathode material. Prepared by the following preparation method.
(1) Dissolving tetrabutyl titanate in a proper amount of glycerol solvent, fully stirring, and adding a certain amount of lanthanum nitrate to ensure that the ratio of Ti: la is 2:1, and then fully stirring is carried out until colorless transparent solution is formed;
(2) reacting LiNi0.8Co0.15Al0.05O2And 2 wt% (relative to the nickel cobalt lithium aluminate) of PVP (polyvinylpyrrolidone) are added into the solution, and the mixture is placed in a constant water bath at the temperature of 80 ℃ to be fully stirred to form a uniform suspensionFloating liquid, wherein the molar ratio of titanium to nickel cobalt lithium aluminate is 2: 100;
(3) adding deionized water dropwise under stirring to slowly hydrolyze tetrabutyl titanate, wherein the molar ratio of the amount of the deionized water to the added titanium source is 2: 1. Fully stirring until the solvent is completely evaporated, and drying the obtained product in an oven at 120 ℃ for 24 hours;
(4) and calcining the obtained coating material at 450 ℃ for 10h to obtain the lithium lanthanum titanate-lithium titanate coated nickel cobalt lithium aluminate anode material.
Example 4
The embodiment provides a lithium lanthanum titanate-lithium titanate coated lithium nickel cobalt aluminate cathode material. Prepared by the following preparation method.
(1) Dissolving tetrabutyl titanate in a proper amount of ethanol solvent, fully stirring, and adding a certain amount of lanthanum acetate to ensure that the ratio of Ti: la is 1:1, and then fully stirring is carried out until colorless transparent solution is formed;
(2) reacting LiNi0.8Co0.15Al0.05O2And 1 wt% (relative to nickel cobalt lithium aluminate) of CTAB (cetyl trimethyl ammonium bromide) was added to the above solution and placed in a constant water bath at 60 ℃ with thorough stirring to form a homogeneous suspension, wherein the molar ratio of titanium to nickel cobalt lithium aluminate was 0.5: 100;
(3) adding deionized water dropwise under stirring to slowly hydrolyze tetrabutyl titanate, wherein the molar ratio of the amount of the deionized water to the added titanium source is 4: 1. Fully stirring until the solvent is completely evaporated, and drying the obtained product in an oven at 100 ℃ for 12 hours;
(4) and calcining the obtained coating material at 650 ℃ for 5 hours to obtain the lithium lanthanum titanate-lithium titanate coated nickel cobalt lithium aluminate anode material.
Example 5
The embodiment provides a lithium lanthanum titanate-lithium titanate coated lithium nickel cobalt aluminate cathode material. Prepared by the following preparation method.
(1) Dissolving tetraisopropyl titanate in a proper amount of ethanol solvent, fully stirring, and adding a certain amount of lanthanum nitrate to ensure that the ratio of Ti: la is 2:1, and then fully stirring is carried out until colorless transparent solution is formed;
(2) reacting LiNi0.815Co0.15Al0.035O2And 2 wt% (relative to nickel cobalt lithium aluminate) of CTAB (cetyl trimethyl ammonium bromide) were added to the above solution and placed in a constant water bath at 80 ℃ and stirred thoroughly to form a homogeneous suspension, wherein the molar ratio of titanium to nickel cobalt lithium aluminate was 1: 100;
(3) adding deionized water dropwise under stirring to slowly hydrolyze tetrabutyl titanate, wherein the molar ratio of the amount of the deionized water to the added titanium source is 4: 1. Fully stirring until the solvent is completely evaporated, and drying the obtained product in an oven at 100 ℃ for 12 hours;
(4) and calcining the obtained coating material at 450 ℃ for 10h to obtain the lithium lanthanum titanate-lithium titanate coated nickel cobalt lithium aluminate anode material.
(I) structural analysis
XRD analysis is carried out on the lithium nickel cobalt aluminate positive electrode material coated by the lanthanum lithium titanate-lithium titanate prepared in the example 1 by using an X-ray instrument, and a test result is shown in figure 1, so that the material has good crystallinity and a good ordered layered structure, and the ratio of a (003) peak to a (104) peak is far greater than 1.2, which shows that the obtained lithium nickel cobalt aluminate positive electrode material has a small cation mixed arrangement degree and is supposed to have good electrochemical performance. Some of the fine diffraction peaks are due to the formation of the cladding layer. To further examine the composition of the coating, we prepared the coating without the addition of lithium nickel cobalt aluminate under the same conditions. Through search, the components of the coating layer are found to be lanthanum lithium titanate and lithium titanate. This demonstrates the success of our introduction of a coating of lanthanum lithium titanate and lithium titanate.
The shape of the lithium nickel cobalt aluminate cathode material coated with the lithium lanthanum titanate-lithium titanate prepared in example 1 was analyzed by a scanning electron microscope, and the test results are shown in fig. 2, from which it can be seen that the prepared lithium nickel cobalt aluminate cathode material has a primary particle of about 500nm and a secondary particle of about 10 μm, and a film-like substance is formed on the surface of the secondary particle, suggesting that a coating layer is introduced on the surface.
Using high power transmission electron microscopy on the sample prepared in example 1The test analysis of the lithium lanthanum titanate-lithium titanate coated nickel cobalt lithium aluminate anode material shows that a coating layer with the thickness of about 4nm is formed on the surface of the material, and clear lattice stripes can be seen in the coating layer. Corresponding to lanthanum lithium titanate and lithium titanate (LiTiO) respectively through retrieval2) A crystal plane of (a). This demonstrates the success of our introduction of a heterostructure of lanthanum lithium titanate-lithium titanate.
The structures and the surface morphologies of the lithium lanthanum titanate-lithium titanate coated lithium nickel cobalt aluminate positive electrode materials prepared in examples 2 to 5 were similar to those of the material prepared in example 1.
(II) analysis of electrochemical Properties and cycling stability Properties
1. Battery preparation
(1) Preparing a battery positive plate: grinding and uniformly mixing a lithium lanthanum titanate-lithium titanate-coated lithium nickel cobalt aluminate positive electrode material, acetylene black and a polyvinylidene fluoride binder according to a mass ratio of 80:13:7, adding a proper amount of solvent NMP (N-methyl pyrrolidone), fully stirring to form viscous slurry, uniformly coating the viscous slurry on the surface of an aluminum foil, drying the viscous slurry for 12 hours in a vacuum drying oven at 120 ℃, and cooling to room temperature to obtain the lithium nickel cobalt aluminate positive electrode sheet.
(2) Assembling the battery: and cutting the obtained battery positive plate into a wafer with the diameter of 14mm by using a slicer, accurately weighing the mass of the wafer, calculating the mass of an active substance in the positive plate according to the formula composition, and assembling the positive plate into a 2025 type testable button battery in a glove box (the oxygen content is less than 0.1ppm, and the water content is less than 0.1ppm) by using a diaphragm with the diameter of 19mm and a metal lithium plate with the diameter of 15 mm.
2. The electrochemical performance test method comprises the following steps:
and (3) carrying out charge and discharge tests on the assembled battery at various multiplying powers by using the Shenzhen Xinwei high-performance battery test system.
The lithium lanthanum titanate-lithium titanate-coated nickel cobalt lithium aluminate positive electrode material obtained in example 1 is assembled into a button 2025 battery by using the half-battery assembly method, and then a Shenzhen new power high performance battery test system is used for performing charge and discharge tests on the battery under various multiplying powers. Under the 0.1C multiplying power, the first charge-discharge test result is shown in figure 4, and it can be seen from the figure that the first discharge capacity is 193.0mAh/g, and the first-cycle coulombic efficiency (the ratio of the specific capacity of discharging gram to the specific capacity of charging gram) is 90.2%. As shown in fig. 5, the capacity retention rate can reach 95% after 100 cycles at 1C; as shown in fig. 6, the capacity retention after 300 cycles was still about 85.0% at 5C magnification.
The lithium lanthanum titanate-lithium titanate-coated lithium nickel cobalt aluminate positive electrode materials obtained in examples 1 to 5 are assembled into a button 2025 battery by using the half-cell assembly method, and then the battery is subjected to charge and discharge tests at various multiplying powers by using a Shenzhen new power battery test system, and the test results are shown in table 1.
Table 1 battery charge and discharge test results at 0.1C and 5C rates
From the analysis, the lithium nickel lanthanum titanate-lithium titanate coated lithium nickel cobalt aluminate cathode material obtained by the preparation method has excellent electrochemical performance and cycle stability.
It will be appreciated by those of ordinary skill in the art that the examples provided herein are intended to assist the reader in understanding the principles of the invention and are to be construed as being without limitation to such specifically recited examples and embodiments. Those skilled in the art can make various other specific changes and combinations based on the teachings of the present invention without departing from the spirit of the invention, and these changes and combinations are within the scope of the invention.
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Effective date of registration: 20220523 Address after: 512721 Building 1, Songtian plant area, Gonghe village committee, Rucheng Town, Ruyuan Yao Autonomous County, Shaoguan City, Guangdong Province Patentee after: Ruyuan dongyangguang new energy material Co.,Ltd. Patentee after: Chengdu University of Technology Address before: 512799 Development Zone, Ruyuan County, Shaoguan City, Guangdong Province Patentee before: RUYUAN DONG YANG GUANG MATERIALS Co.,Ltd. Patentee before: Chengdu University of Technology |