CN114864895B - Surface-reconstructed lithium-rich manganese-based positive electrode material, and preparation method and application thereof - Google Patents
Surface-reconstructed lithium-rich manganese-based positive electrode material, and preparation method and application thereof Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 69
- 239000011572 manganese Substances 0.000 title claims abstract description 69
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 59
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 57
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011247 coating layer Substances 0.000 claims abstract description 24
- 239000013590 bulk material Substances 0.000 claims abstract description 23
- 239000010410 layer Substances 0.000 claims abstract description 23
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 21
- -1 zirconium alkoxide Chemical class 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 24
- 239000000725 suspension Substances 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 11
- 239000010405 anode material Substances 0.000 claims description 9
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims description 2
- UARGAUQGVANXCB-UHFFFAOYSA-N ethanol;zirconium Chemical compound [Zr].CCO.CCO.CCO.CCO UARGAUQGVANXCB-UHFFFAOYSA-N 0.000 claims description 2
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 17
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- 238000012360 testing method Methods 0.000 description 14
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- 239000011248 coating agent Substances 0.000 description 12
- 230000005012 migration Effects 0.000 description 12
- 238000013508 migration Methods 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 9
- 230000007062 hydrolysis Effects 0.000 description 9
- 238000006460 hydrolysis reaction Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 229910008555 Li1.2Mn0.6Ni0.2O2 Inorganic materials 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 239000010416 ion conductor Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- MKGYHFFYERNDHK-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Ti+4].[Li+] Chemical compound P(=O)([O-])([O-])[O-].[Ti+4].[Li+] MKGYHFFYERNDHK-UHFFFAOYSA-K 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 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 description 2
- 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 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
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- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000002033 PVDF binder Substances 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
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
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- 229910052786 argon Inorganic materials 0.000 description 1
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- 238000009831 deintercalation Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
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- 230000002427 irreversible effect Effects 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 229940071257 lithium acetate Drugs 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000011866 long-term treatment Methods 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 230000003442 weekly effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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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- C01—INORGANIC CHEMISTRY
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- C01G53/00—Compounds of nickel
- C01G53/40—Complex oxides containing nickel and at least one other metal element
- C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
- C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
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- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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Abstract
The invention discloses a surface-reconstructed lithium-rich manganese-based positive electrode material, and a preparation method and application thereof, wherein the surface-reconstructed lithium-rich manganese-based positive electrode material comprises a body material and a coating layer coated on the surface of the body material, and the chemical formula of the lithium-rich manganese-based positive electrode material is mZrO 2 @nLi 2 ZrO 3 @Li 1+x M 1‑x‑ y Zr y O 2 M is one or more of Ni, co and Mn, x is more than 0 and less than 1, and m+n+y is more than 0 and less than 0.03. The method utilizes the characteristic that zirconium alkoxide can hydrolyze in deionized water to generate ZrO on the surface of the bulk material 2 Coating layer, and generating Li by residual alkali on surface of bulk material 2 ZrO 3 Layer, li 2 ZrO 3 Zr in the coating layer can migrate inwards under the thermodynamic action, so that near-surface doping of Zr is formed, the three-in-one surface can be constructed through a simple wet chemical method and a high-temperature solid phase method, the process is simple, the production efficiency is high, the reaction condition is easy to control, and the material after surface reconstruction according to the method has higher circulation stability and multiplying power performance and is easy for commercial mass production.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a surface-reconstructed lithium-rich manganese-based positive electrode material, and a preparation method and application thereof.
Background
The rapid development of new energy industry has increased scientists' development of high specific energy positive electrode materials to improve the performance of batteries to meet the needs of people. Layered lithium-rich manganese-based cathode materials are considered to be one of the most potential cathode materials due to their ultra-high theoretical capacity (> 250 mAh/g), low cost. In order to realize 'lithium enrichment', excessive lithium salt is added in the synthesis process, so that the alkalinity of the surface of the material is enhanced, the reactivity is correspondingly improved, and various side reactions with electrolyte can occur. In addition, the high capacity of lithium-rich materials also results from the redox of anions, which can lead to irreversible oxygen release, oxidative decomposition of the electrolyte and transition metal migration leading to phase changes. The phase change of the positive electrode material itself can form vicious circle with the side reaction of the electrolyte, and finally the circulation performance and the multiplying power performance of the material are deteriorated.
In order to reduce side reactions of the electrode surface with the electrolyte and to increase the cycle life of the cathode material, the most straightforward approach is to coat the passivation layer with, for example, al 2 O 3 、ZnO、ZrO 2 Etc., and in order to reduce oxygen release and transition metal migration, metallic elements with stronger bond energy are generally introduced, so that the cation mixing and discharging can be reduced to play a role in stabilizing the material structure, and common elements are Al, mg and Zr.
However, the two methods of the prior art do not achieve synergy or require the use of complex methods to combine the two. Therefore, a simple, flexible and multi-purpose surface reconstruction method is needed to comprehensively improve the electrochemical performance.
The applicant discloses a surface aluminum doping and titanium aluminum lithium phosphate coated lithium-rich manganese-based positive electrode material and a preparation method thereof in a prior patent CN111987297A, wherein the patent utilizes aluminum nitrate to decompose and generate bi-directional migration of Al in a high-temperature calcination process, the bi-directional migration of Al is formed by migration to the inside of a lithium-rich manganese-based positive electrode material body, the surface Al doping is formed, the counter migration is formed in the titanium lithium phosphate coated by an outer layer, the fast ion conductor titanium aluminum lithium phosphate is formed, and meanwhile, ti in the titanium lithium phosphate on the outer layer 4+ And also diffuses inward. The coating layer can prevent the positive electrode material from directly contacting with the electrolyte, generate side reaction and inhibit the phase change of the lithium-rich manganese-based positive electrode material, thereby effectively improving the lithium-rich manganese-based positive electrode materialThe first week coulomb efficiency of the material and the cycle performance are improved. However, in practical application, the technology cannot effectively solve the problem of voltage drop of the lithium-rich manganese-based positive electrode material, and the obtained lithium ion battery has a voltage range of 2.0V-4.6V and a voltage of 1C (1C=250mAh.g) -1 ) Under test conditions of charge-discharge current, the average weekly voltage decay after 50 weeks of cycling was shown to be 2.9-3.5mV. Meanwhile, the technology is only suitable for laboratory application, and when the technology is used for mass commercial production, tetrabutyl titanate is used for coating, the tetrabutyl titanate cannot be contacted with water, otherwise, hydrolysis can occur to produce titanium dioxide so as to reduce the ionic conductivity of a coating layer, so that high requirements are put on raw material preservation and production environment, the mass production cost is high, and the technology still needs to be realized by using a complex method.
Disclosure of Invention
The invention aims at: aiming at the problems, the invention provides the surface-reconstructed lithium-rich manganese-based positive electrode material, and the preparation method and application thereof.
The technical scheme adopted by the invention is as follows: a surface-reconstructed lithium-rich manganese-based positive electrode material comprises a body material and a coating layer coated on the surface of the body material, wherein the chemical formula of the lithium-rich manganese-based positive electrode material is mZrO 2 @nLi 2 ZrO 3 @Li 1+ x M 1-x-y Zr y O 2 M is one or more of Ni, co and Mn, x is more than 0 and less than 1, and m+n+y is more than 0 and less than 0.03.
Further, the coating layer on the surface of the body material is ZrO 2 A layer of ZrO 2 The interface between the layer and the bulk material is provided with Li 2 ZrO 3 And a layer, the surface or near surface of the bulk material being doped with Zr.
Further, the molar ratio of zirconium to the bulk material is 0.1-3.0%.
Further, the invention also discloses a preparation method of the surface-reconstructed lithium-rich manganese-based positive electrode material, which comprises the following steps:
A. taking a lithium-rich manganese-based positive electrode body material, and mixing the body material with deionized water and absolute ethyl alcohol to form a uniform suspension A;
B. dissolving zirconium alkoxide in absolute ethyl alcohol to form a solution B;
C. dropwise adding the suspension A into the solution B with a corresponding amount, continuously stirring and dispersing, and then carrying out water bath and stirring until the suspension A is dried to obtain powder;
D. and (3) placing the powder in a muffle furnace for calcination to obtain the lithium-rich manganese-based anode material with the surface reconstructed.
In the preparation method of the invention, by utilizing the characteristic that zirconium alkoxide can hydrolyze in deionized water, zrO can be generated on the surface of a bulk material by adding suspension A containing deionized water and the bulk material into zirconium alkoxide solution 2 Coating, zrO 2 After the formation of the coating layer, zrO will be caused by the existence of residual alkali (excessive Li) on the surface of the bulk material 2 The coating layer can react with residual alkali on the surface of the bulk material to generate Li 2 ZrO 3 Thereby constructing a layer of Li on the surfaces of the coating layer and the bulk material 2 ZrO 3 Layer, li 2 ZrO 3 Has chemical and electrochemical stability, and simultaneously has higher lithium ion migration rate to generate Li 2 ZrO 3 The coating layer is favorable for ion migration of the interface. Meanwhile, under the subsequent calcination effect, li 2 ZrO 3 Zr in the coating layer can migrate inwards under the thermodynamic action, so that near-surface doping of Zr is formed, oxygen release and transition metal migration on the surface of the positive electrode material can be restrained by the near-surface doping of Zr, voltage attenuation can be effectively reduced, and cycle stability is improved. For the outermost layer ZrO of the outermost layer 2 Coating, zrO 2 The coating layer can play a role in physical protection as an oxide passivation layer, so that side effects of the electrolyte are relieved. Therefore, the preparation method realizes the preparation of the lithium-rich manganese-based anode material with a multifunctional interface phase, which is similar to the prior artCompared with the prior art, the invention can construct the three-in-one surface by a simple wet chemical method and a high-temperature solid phase method, has simple process, high production efficiency and easily controlled reaction conditions.
In the present invention, the hydrolysis rate of zirconium alkoxide is critical, and if the hydrolysis rate is too slow, coating efficiency and production are low, and if the hydrolysis rate is too fast, zrO is generated on the surface of the bulk material 2 ZrO in the case of coating 2 The residual alkali on the surface of the bulk material does not react with the bulk material, and Li is difficult to be generated 2 ZrO 3 Layers or formation of Li with extremely uneven distribution 2 ZrO 3 Layer, zrO 2 The ionic conductivity of the coating layer is generally not obvious to improve the multiplying power performance of the positive electrode material, and when Zr is required to diffuse to the surface of the bulk material, a high temperature is required to destroy ZrO 2 Not only puts new demands on the process, but also the ZrO of the bulk material surface 2 The structural stability of the coating is also compromised, resulting in an affected final stability of the material. Accordingly, if Li with uneven distribution is generated 2 ZrO 3 A layer of unevenly distributed Li 2 ZrO 3 The layer also significantly reduces the improvement in the rate capability, structural stability, and pressure drop of the coating layer to the material. Therefore, the rate of hydrolysis of zirconium ions is important, and it is relevant to whether the present invention can build a "three-in-one" surface. According to the invention, the hydrolysis rate of zirconium ions can be controlled by limiting the molar ratio of zirconium ions to deionized water, when the molar ratio of deionized water to zirconium alkoxide in suspension A is 1-2:1, a proper three-in-one surface can be constructed, for example, the molar ratio of the deionized water to zirconium alkoxide in suspension A can be 1:1, 1.2:1, 1.3:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2.0:1 and the like, and the three-in-one surface of the application is difficult to obtain if the molar ratio exceeds the ratio range, or the obtained technical effect is poor and the practical value is not high.
Further, in the present invention, in addition to controlling the hydrolysis rate of zirconium ions, it is also necessary to control the degree of hydrolysis of zirconium ions, and only a proper coating amount is obtained on the surface of the bulk material to obtain a preferable performance,for example, when the degree of hydrolysis is too large, resulting in an excessively high coating amount, the coating amount is too high due to ZrO 2 The coating layer has no electrochemical activity, the capacity cannot be provided, and the density capacity of the material can be influenced by the excessive coating amount, so that the coating layer is obtained through test conclusion, and in the step C, the stirring reaction time is preferably 0.5-2.0h, and the positive electrode material with excellent performance is not obtained easily due to the excessively short or excessively long stirring reaction time.
Further, the temperature rising rate during calcination is 1-5 ℃/min, the calcination temperature is 500-800 ℃, and the calcination time is 3-8h.
Further, the zirconium alkoxide is one or more of zirconium n-butoxide, zirconium isopropoxide, zirconium n-propoxide and zirconium ethoxide, and can be selected according to actual requirements.
The invention further provides an application of the surface-reconstructed lithium-rich manganese-based positive electrode material in a lithium battery, wherein the lithium battery comprises a positive electrode, a battery diaphragm and a negative electrode, the positive electrode comprises a positive electrode active material, and the positive electrode active material is the surface-reconstructed lithium-rich manganese-based positive electrode material.
In summary, due to the adoption of the technical scheme, the beneficial effects of the invention are as follows:
1. the method utilizes the characteristic that zirconium alkoxide can hydrolyze in deionized water to generate ZrO on the surface of the bulk material 2 Coating layer, and generating Li by residual alkali on surface of bulk material 2 ZrO 3 Layer, then under calcination, li 2 ZrO 3 Zr in the coating layer migrates inwards under the thermodynamic action, thereby forming near-surface doping of Zr, zrO 2 The coating layer can play a role in physical protection as an oxide passivation layer, so that the side reaction of electrolyte is relieved, li 2 ZrO 3 The coating layer has chemical and electrochemical stability, and has higher lithium ion migration rate, so that the ion migration of an interface is facilitated after the coating layer is generated, the near-surface doping of Zr can inhibit the oxygen release and transition metal migration of the surface of the anode material, thereby effectively reducing voltage attenuation and further improving the circulation stability;
2. according to the invention, the three-in-one surface is constructed on the lithium-rich manganese-based positive electrode material, so that the cycle stability, the multiplying power performance and the pressure drop performance of the material are improved, and the obtained positive electrode material has excellent comprehensive performance and huge commercialization potential;
3. the preparation method provided by the invention realizes the preparation of the lithium-rich manganese-based positive electrode material with a multifunctional interface phase, has the advantages of simple process, high production efficiency, good quality stability of finished products and easily controlled reaction conditions, and is especially suitable for large-scale commercial production.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of examples 1,2,3, 4;
FIG. 2 is a Scanning Electron Microscope (SEM) image of example 1;
FIG. 3 is a Scanning Electron Microscope (SEM) image of example 2;
FIG. 4 is a Scanning Electron Microscope (SEM) image of example 3;
FIG. 5 is a Scanning Electron Microscope (SEM) image of example 4;
FIG. 6 is a graph of the discharge capacity of the assembled coin cell of example 1 with unmodified material at 30℃for 50 weeks at 1C;
FIG. 7 is an alternating current impedance (EIS) diagram of a button cell assembled with unmodified materials of example 2;
FIG. 8 is a graph comparing the rate performance of the button cell assembled from example 3 and unmodified materials;
fig. 9 is a medium voltage discharge plot for a coin cell assembled with unmodified material of example 4 at 30C for 50 weeks at 1C.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings.
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The following examples and comparative examples consisted of test cells in the following manner:
and (3) battery assembly: li before and after modification prepared in examples 1.2 Ni 0.2 Mn 0.6 O 2 As an active material, mixing the active material with acetylene black and PVDF (polyvinylidene fluoride) according to the mass ratio of 8:1:1, adding NMP, grinding into slurry, coating the slurry on aluminum foil by using a scraper, drying, and cutting into a positive plate; then, the CR2025 button half-cell is assembled in an argon glove box (water is less than 0.01ppm, oxygen is less than 0.01 ppm), wherein the positive electrode is the positive electrode plate, the counter electrode is a lithium plate, the diaphragm is Celgard 2500, the electrolyte is prepared from dimethyl carbonate, diethyl carbonate and ethyl carbonate with the volume ratio of 1:1:1 as solvents, and 1mol/L of LiPF is adopted 6 Is a solution made of solute.
The material characterization analysis method comprises the following steps:
x-ray diffractometer: rigaku Ultima IV-185, japan;
scanning electron microscope test: FEI Quanta, netherlands;
battery cycle performance test: lanD CT 2001A tester was purchased from Wuhan City blue electric Co., ltd;
alternating current impedance test: CHI604D was purchased from Shanghai Chen Hua instruments Co.
Example 1
The preparation method of the surface-reconstructed lithium-rich manganese-based positive electrode material comprises the following steps of:
s1, will be 0.5. 0.5gLi 1.2 Mn 0.6 Ni 0.2 O 2 Mixing and stirring the lithium-rich manganese-based positive electrode material with 10mL of absolute ethyl alcohol and 0.001g of deionized water to obtain uniform suspension A;
s2, dissolving 0.0137g of zirconium n-propoxide solution (70 wt%) in 10mL of absolute ethanol to form a solution B;
s3, dropwise adding the suspension A into the solution B, continuously stirring and reacting for 0.5h, then carrying out water bath at 60 ℃ and stirring until the solution A is dried to obtain powder;
and S4, placing the powder in a muffle furnace, heating to 500 ℃ at a speed of 5 ℃/min, and calcining for 5 hours to obtain the lithium-rich manganese-based positive electrode material with the surface reconstructed.
The structure and electrochemical performance of the lithium-rich manganese-based positive electrode materials before and after modification in this example were tested, and specific test results are as follows:
fig. 1 is a graph obtained by performing X-ray diffraction (XRD) on a material, and as can be seen from fig. 1, the diffraction peak of the material coincides with the peak position of a common lithium-rich material, and the sharp peak shape indicates that the material has good crystallinity. FIG. 2 is a treated mZrO 2 @nLi 2 ZrO 3 @Li 1.2 Mn 0.6 Ni 0.2-y Zr y O 2 SEM image of the positive electrode material (m+n+y=0.005) by scanning electron microscope, it can be seen from fig. 2 that the morphology of the material is polygonal, the particle size is uniform, and the diameter is 200-400nm.
Further, the material was assembled into a battery, charged and discharged at a rate of 0.1C (1c=250 mA/g) for 2 weeks, and then cycled at a rate of 1C for 50 weeks, and the test results are shown in fig. 6. As can be seen from fig. 6, at a 1C rate, the first-week discharge specific capacity of the coated material was 182.4mAh/g, which is slightly lower than 196.7mAh/g of the material of comparative example 1, because the coated material does not have electrochemical activity and cannot provide capacity, but the difference between the two materials can be clearly seen after 50 weeks of circulation, the capacity retention rate of the coated material is 88.21%, and the material of comparative example 1 is only 41.38%, so that the coating process of the present invention optimizes the material circulation performance.
Example 2
The preparation method of the surface-reconstructed lithium-rich manganese-based positive electrode material comprises the following steps of:
s1, will be 0.5. 0.5gLi 1.2 Mn 0.6 Ni 0.2 O 2 Mixing and stirring the lithium-rich manganese-based anode material with 10mL of absolute ethyl alcohol and 0.0032g of deionized water to obtain a uniform suspension A;
s2, dissolving 0.0413g of zirconium n-propoxide solution (70 wt%) in 10mL of absolute ethanol to form a solution B;
s3, dropwise adding the suspension A into the solution B, continuously stirring and reacting for 2 hours, then carrying out water bath at 60 ℃ and stirring until the mixture is dried to obtain powder;
and S4, placing the powder in a muffle furnace, heating to 600 ℃ at a speed of 5 ℃/min, and calcining for 6 hours to obtain the lithium-rich manganese-based anode material with the surface reconstructed.
The structure and electrochemical performance of the lithium-rich manganese-based positive electrode materials before and after modification in this example were tested, and specific test results are as follows:
fig. 1 is the result of XRD test performed in example 2, and it can be seen from fig. 1 that the peak of the material is split clearly, the peak shape is sharp, the crystallinity of the material is good, and the layered structure is obvious. FIG. 3 is a surface morphology observed under SEM of the material of example 2. As can be seen from FIG. 3, the surface material becomes rough with increasing addition amount of zirconium source and reaction time, because with ZrO 2 The increase in the content and reaction time, in addition to reacting with the surface residual lithium, also has partially deposited ZrO 2 The surface will be rougher. The treated positive electrode material mZrO 2 @nLi 2 ZrO 3 @Li 1.2 Mn 0.6 Ni 0.2-y Zr y O 2 (m+n+y=0.015) assembled into a coin cell was subjected to an ac impedance test, and as a result, as shown in the Nyquist diagram of fig. 7, in fig. 7, it was constituted by a semicircle in the high frequency region, which is mainly controlled in charge transfer, and a straight line in the low frequency region, which is controlled by diffusion of the reactant or product, and as can be seen from comparison of fig. 7, the treated sample of example 2 had a smaller charge transfer impedance due to ZrO 2 React with residual alkali on the surface of the material to generate an ion conductor Li 2 ZrO 3 This helps to improve the conductivity and rate performance of the material. Further, the first week specific capacity of the material at 1C rate is 176.1mAh/g, and the capacity retention rate after 50 weeks circulation is 89.00%.
Example 3
The preparation method of the surface-reconstructed lithium-rich manganese-based positive electrode material comprises the following steps of:
s1, will be 0.5. 0.5gLi 1.2 Mn 0.6 Ni 0.2 O 2 Mixing and stirring the lithium-rich manganese-based anode material with 10mL of absolute ethyl alcohol and 0.0016g of deionized water to obtain uniform suspension A;
s2, dissolving 0.0413g of zirconium n-propoxide solution (70 wt%) in 10mL of absolute ethanol to form a solution B;
s3, dropwise adding the suspension A into the solution B, continuously stirring and reacting for 1h, then carrying out water bath at 60 ℃ and stirring until the solution A is dried to obtain powder;
and S4, placing the powder in a muffle furnace, heating to 700 ℃ at a speed of 5 ℃/min, and calcining for 7 hours to obtain the lithium-rich manganese-based positive electrode material with the surface reconstructed.
The structure and electrochemical performance of the lithium-rich manganese-based positive electrode materials before and after modification in this example were tested, and specific test results are as follows:
the crystal structure of the material is characterized, and the result is shown in an XRD chart of fig. 1, and as can be seen from fig. 1, the material shows a traditional lithium-rich diffraction peak, and the crystal structure is complete and free of impurity peaks, so that the modification treatment does not cause structural change. Fig. 4 is a representation of the surface topography of a material, as can be seen from fig. 4, that the material surface becomes rougher, which is related to the material being processed at higher temperatures. The modified material mZrO 2 @nLi 2 ZrO 3 @Li 1.2 Mn 0.6 Ni 0.2-y Zr y O 2 (m+n+y=0.015) and comparative example 1 materials were assembled into batteries, respectively, and charge and discharge tests were performed at 0.2C, 0.5C, 1C, 2C and 5C to compare the rate performance thereof. As a result, as shown in fig. 8, it can be seen from fig. 8 that the rate performance of the treated material is superior to that of the bulk material. The capacity of the material decays due to polarization, and returns to a low current capacity to recover a part, and it can be seen from comparison that the capacity of example 3 is higher than that of the sample of comparative example 1, both at high current and low current densities, due to the formation of fast ionic conductor Li on the surface of the material 2 ZrO 3 A layer, further improving the ion transmission efficiency of the interface, and simultaneously adding high temperature effect and Zr on the surface 4+ The doped material is used as a support between lithium layers, the interlayer distance is enlarged, and the deintercalation of lithium ions is accelerated, so that the multiplying power performance of the material is improved, and higher capacity can still be released under high multiplying power. Further, the first week specific capacity 187.9mAh/g of the material under the 1C multiplying power, and the capacity retention rate after 50 weeks circulation is 85.90%.
Example 4
The preparation method of the surface-reconstructed lithium-rich manganese-based positive electrode material comprises the following steps of:
s1, will be 0.5. 0.5gLi 1.2 Mn 0.6 Ni 0.2 O 2 Mixing and stirring the lithium-rich manganese-based anode material with 10mL of absolute ethyl alcohol and 0.0032g of deionized water to obtain a uniform suspension A;
s2, dissolving 0.0825g of zirconium n-propoxide solution (70 wt%) in 10mL of absolute ethanol to form a solution B;
s3, dropwise adding the suspension A into the solution B, continuously stirring and reacting for 0.5h, then carrying out water bath at 60 ℃ and stirring until the solution A is dried to obtain powder;
and S4, placing the powder in a muffle furnace, heating to 800 ℃ at a speed of 5 ℃/min, and calcining for 8 hours to obtain the lithium-rich manganese-based positive electrode material with the surface reconstructed.
The structure and electrochemical performance of the lithium-rich manganese-based positive electrode materials before and after modification in this example were tested, and specific test results are as follows:
as shown in the XRD chart of FIG. 1, the original crystal structure of the lithium-rich manganese-based positive electrode material synthesized in the embodiment 4 is not changed, and the ratio of the (003) crystal face intensity to the (104) crystal face intensity is greater than 1.2, which indicates that the material has less cation mixing and stable crystal structure. Fig. 5 is a surface morphology display of example 4, and it can be seen from SEM characterization that the material particles are more uniform in size and about 200nm in size after long-term treatment at high temperature. For lithium-rich materials, in addition to the capacity fade, the change in oxygen release and crystal structure can also cause a decay in the discharge voltage, which has a greater impact on the energy density of the material. Thus, the positive electrode material mZrO as treated in example 4 2 @nLi 2 ZrO 3 @Li 1.2 Mn 0.6 Ni 0.2-y Zr y O 2 The materials of (m+n+y=0.03) and comparative example 1 were assembled into a battery, respectively, and subjected to a 1C charge-discharge cycle test, and the discharge medium voltage was compared with the cycle number change, and as a result, as shown in fig. 9, it can be seen from fig. 9 that the treated material not only increased the discharge medium voltage, but also alleviated the voltage decay, and the average voltage was 2.198mV per week, which was far lower than 11.124mV of the sample of comparative example 1. This is due to the increase in ZrO 2 More Zr in the treatment capacity and reaction temperature 4+ Into the crystal lattice, zr-O has higher bond energy, thus increasing the voltage required for the reaction, and Zr 4+ The introduction of the catalyst reduces Li/Ni mixed discharge and maintainsThe structure is stable, so that voltage attenuation can be reduced in the circulation process, and the electrochemical performance of the battery is improved. Further, the first week specific capacity 191.9mAh/g of the material under the 1C multiplying power, and the capacity retention rate after 50 weeks circulation is 89.16%.
Comparative example 1
Untreated sample, i.e. with Li 1.2 Mn 0.6 Ni 0.2 O 2 As a sample of comparative example 1, a lithium-rich manganese-based positive electrode material was prepared comprising the steps of:
s1, weighing lithium acetate, manganese acetate and nickel acetate according to a molar ratio of 1.2:0.6:0.2, and adding distilled water for dissolution to obtain a mixed salt solution;
s2, dropwise adding a citric acid solution into the mixed salt solution, and then adjusting the pH value to 7.8 by using ammonia water to obtain a mixed solution;
s3, heating the mixed solution to gel at 80 ℃, vacuum drying at 80 ℃ for 40 hours, placing in an oxygen atmosphere in a muffle furnace, firstly heating to 500 ℃ for calcination for 6 hours, and then heating to 800 ℃ for calcination for 14 hours to obtain the lithium-rich manganese-based layered material Li 1.2 Mn 0.6 Ni 0.2 O 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein, the mol ratio of the citric acid to the transition metal ions is 1:1, and the temperature rising rate during calcination is 5 ℃/min.
The lithium battery assembled by the sample has a first-week discharge specific capacity of 196.7mAh/g at 30 ℃ and 1C, and a cycle 50 week retention rate of 41.38%.
Comparative example 2
Zr alone in the sample 4+ Doping, comprising the following steps:
s1, dissolving 0.0413g of zirconium n-propoxide solution (70 wt%) in 10mL of absolute ethanol to form a solution A;
s2, mixing 0.5g of finished product Li 1.2 Mn 0.6 Ni 0.2 O 2 Adding into the solution A, continuously stirring and reacting for 10min, then carrying out water bath at 60 ℃ and stirring until the solution A is dried to obtain powder;
and S3, placing the powder in a muffle furnace, heating to 800 ℃ at a speed of 5 ℃/min, and calcining for 8 hours to obtain the modified lithium-rich manganese-based anode material.
The lithium battery assembled by the sample has the first cycle discharge specific volume at 30 ℃ and 1 DEG CThe amount was 199.4mAh/g, and the retention rate was 59.53% after 50 weeks of circulation. Thus, only Zr is performed 4+ Doping has limited improvement of the cyclic stability of the material, and high requirements are difficult to meet.
Comparative example 3
By ZrO only 2 The coating comprises the following steps:
s1, will be 0.5. 0.5gLi 1.2 Mn 0.6 Ni 0.2 O 2 Mixing the finished product with 10mL of deionized water, and stirring to obtain uniform suspension A;
s2, dropwise adding the suspension A into 0.0413g of zirconium n-propoxide solution (70 wt%) and continuously stirring for reaction for 10min, then carrying out water bath at 60 ℃ and stirring until the mixture is dried to obtain powder;
and S3, placing the powder in a muffle furnace, heating to 500 ℃ at a speed of 5 ℃/min, and calcining for 5 hours to obtain the coated lithium-rich manganese-based positive electrode material.
The materials are active materials, the initial cycle discharge specific capacity of the assembled battery at 30 ℃ and 1C is 163.4mAh/g, and the cycle 50 week retention rate is 86.59%. Thus, it is possible to obtain ZrO only 2 Cladding reduces the capacity properties of the material.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (7)
1. The surface-reconstructed lithium-rich manganese-based positive electrode material comprises a body material and a coating layer coated on the surface of the body material, and is characterized in that the chemical formula of the lithium-rich manganese-based positive electrode material is mZrO 2 @nLi 2 ZrO 3 @Li 1+x M 1-x-y Zr y O 2 M is one or more of Ni, co and Mn, x is more than 0 and less than 1, and m+n+y is more than 0 and less than 0.03; the preparation method of the lithium-rich manganese-based positive electrode material comprises the following steps of:
A. taking a lithium-rich manganese-based positive electrode body material, and mixing the body material with deionized water and absolute ethyl alcohol to form a uniform suspension A;
B. dissolving zirconium alkoxide in absolute ethyl alcohol to form a solution B;
C. dropwise adding the suspension A into a solution B with a corresponding amount, continuously stirring and dispersing the suspension A in a molar ratio of deionized water to zirconium alkoxide of 1-2:1, and then carrying out water bath and stirring until the suspension A is dried to obtain powder;
D. and (3) placing the powder in a muffle furnace for calcination to obtain the lithium-rich manganese-based anode material with the surface reconstructed.
2. The surface-reconstituted lithium-rich manganese-based positive electrode material according to claim 1, wherein the coating layer on the surface of the bulk material is ZrO 2 A layer of ZrO 2 The interface between the layer and the bulk material is provided with Li 2 ZrO 3 And a layer, the surface or near surface of the bulk material being doped with Zr.
3. The surface-reconstituted lithium-rich manganese-based positive electrode material according to claim 1 or 2, wherein the molar ratio of zirconium to the bulk material is 0.1-3.0%.
4. The surface-reconstituted lithium-rich manganese-based positive electrode material according to claim 3, wherein in step C, the stirring reaction is performed for a time of 0.5 to 2.0 hours.
5. The surface-reconstituted lithium-rich manganese-based positive electrode material according to claim 4, wherein in step D, the temperature rise rate upon calcination is 1 to 5 ℃/min, the calcination temperature is 500 to 800 ℃, and the calcination time is 3 to 8 hours.
6. The surface-reconstituted lithium-rich manganese-based positive electrode material according to claim 1, wherein the zirconium alkoxide is one or more of zirconium n-butoxide, zirconium isopropoxide, zirconium n-propoxide, zirconium ethoxide.
7. Use of a surface-reconstituted lithium-rich manganese-based positive electrode material in a lithium battery comprising a positive electrode, a battery separator and a negative electrode, the positive electrode comprising a positive electrode active material, characterized in that the positive electrode active material is the lithium-rich manganese-based positive electrode material of claim 6.
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