CN102931394B - Lithium nickel manganese oxide material and preparation method thereof, lithium ion battery containing this material - Google Patents
Lithium nickel manganese oxide material and preparation method thereof, lithium ion battery containing this material Download PDFInfo
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- CN102931394B CN102931394B CN201210472464.3A CN201210472464A CN102931394B CN 102931394 B CN102931394 B CN 102931394B CN 201210472464 A CN201210472464 A CN 201210472464A CN 102931394 B CN102931394 B CN 102931394B
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- 239000000463 material Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229910001416 lithium ion Inorganic materials 0.000 title abstract description 32
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title abstract description 30
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 title abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 66
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000011572 manganese Substances 0.000 claims abstract description 53
- 239000002131 composite material Substances 0.000 claims abstract description 39
- 238000001556 precipitation Methods 0.000 claims abstract description 35
- 239000011259 mixed solution Substances 0.000 claims abstract description 33
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 28
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 23
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 150000002696 manganese Chemical class 0.000 claims abstract description 10
- 150000002815 nickel Chemical class 0.000 claims abstract description 10
- 229910012752 LiNi0.5Mn0.5O2 Inorganic materials 0.000 claims description 41
- 229910013716 LiNi Inorganic materials 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 24
- 229910052748 manganese Inorganic materials 0.000 claims description 20
- 229910052759 nickel Inorganic materials 0.000 claims description 19
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 17
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 10
- 229910001437 manganese ion Inorganic materials 0.000 claims description 10
- 229910001453 nickel ion Inorganic materials 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 8
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 8
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 6
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- 239000011565 manganese chloride Substances 0.000 claims description 6
- 235000002867 manganese chloride Nutrition 0.000 claims description 6
- 229940099607 manganese chloride Drugs 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 229940071125 manganese acetate Drugs 0.000 claims description 5
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 5
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 29
- 238000000975 co-precipitation Methods 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 239000013078 crystal Substances 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 10
- 238000002156 mixing Methods 0.000 abstract description 8
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 150000001768 cations Chemical class 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 32
- 238000003756 stirring Methods 0.000 description 20
- 239000000203 mixture Substances 0.000 description 17
- 238000000498 ball milling Methods 0.000 description 16
- 238000001035 drying Methods 0.000 description 16
- 238000001354 calcination Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000007599 discharging Methods 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 8
- 239000008247 solid mixture Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 5
- 238000009413 insulation Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000011017 operating method Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910006703 Li—Ni—Mn—O Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229940072033 potash Drugs 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 238000005118 spray pyrolysis Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- -1 ethyl carbonate ester Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of preparation method of lithium nickel manganese oxide material, comprise the following steps: (1) by nickel salt and manganese salt according to stoichiometric proportion Ni: Mn=1: 1 to configure the mixed solution of nickel salt and manganese salt, in mixed solution, add the precipitation reagent of excessive 2 ~ 6%, obtain nickel manganese compound carbonate precipitation or nickel-manganese composite hydroxide precipitation; (2) lithium nickel manganese oxide material is prepared with the compound of lithium and nickel manganese compound carbonate or nickel-manganese composite hydroxide.This preparation method's technique is simple, and coprecipitation process does not need to control the pH value in course of reaction, thus makes coprecipitation process be very easy to control, and the method is applicable to industrialization large-scale production.Cation mixing in the crystal structure of the lithium nickel manganese oxide material prepared by the method is reduced, thus improves the chemical property of lithium ion in charge and discharge process.The lithium ion battery obtained by this lithium nickel manganese oxide material has good cycle performance and high rate performance.
Description
Technical field
The invention belongs to technical field of lithium ion, the lithium ion battery being specifically related to a kind of lithium nickel manganese oxide material and preparation method thereof and using this material to prepare.
Background technology
The plurality of advantages such as energy density is high, voltage platform is high owing to having for lithium ion battery, long service life, self discharge is little, memory-less effect, operating temperature range are wide, environmentally safe, are widely used in the portable electric appts such as mobile communications tool, camera, notebook computer.Cobalt system positive electrode is because of reasons such as cobalt resource is rare, expensive, toxic contaminants environment, and people make great efforts in its substitute of searching always; Although LiMn2O4 promoter manganese is abundant, price is relatively cheap, and safety non-pollution, the problems such as its high temperature circulation poor stability, capacity attenuation are serious, affect its commercial applications; LiFePO4, because of reasons such as energy density is low, poor electric conductivity, is not suitable in portable type electronic product.Find after deliberation, laminated Li-Ni-Mn-O positive electrode LiNi
0.5mn
0.5o
2there is the advantage such as higher theoretical specific capacity (276mAh/g), preferably thermodynamic stability, cheap, nontoxic pollution-free, and with LiNiO
2and LiMnO
2the chemical property advantage of material, becomes the study hotspot of current lithium ion secondary battery anode material.
The main preparation methods of current laminated Li-Ni-Mn-O material has coprecipitation, solid phase method, sol-gal process, freeze-drying, ion-exchange, spray pyrolysis etc.Wherein, the general particle of product of sol-gel process synthesis is tiny, and even particle size distribution, crystal property is good, and initial capacity is higher, but synthesis material generally adopts organic reagent, and cost is higher, is difficult to practical application.Solid phase method can realize industrialization large-scale production, and operating procedure is simple, but the particle of the material of preparation is large, and the factors such as uniformity is poor all can have influence on the chemical property of material, thus cause the chemical property of material poor.Freeze-drying, ion-exchange, spray pyrolysis step are complicated and cost is high, are therefore only limited to laboratory research, are unfavorable for practical application.Need in existing Co-precipitation to control the pH value in coprecipitation reaction process, and the very difficult control of precipitation reaction process, the poor-performing of the lithium nickel manganese oxide material therefore prepared.
Summary of the invention
Technical problem to be solved by this invention is for above shortcomings in prior art, provides a kind of LiNi
0.5mn
0.5o
2material and preparation method thereof and the lithium ion battery using this material to prepare, this preparation method's technique is simple, coprecipitation process is very easy to control, and decreases LiNi
0.5mn
0.5o
2cation mixing in crystal structure, improves the LiNi of preparation
0.5mn
0.5o
2material electrochemical performance.
The technical scheme that solution the technology of the present invention problem adopts is to provide a kind of LiNi
0.5mn
0.5o
2the preparation method of material, comprises the following steps:
(1) nickel salt and manganese salt are configured the mixed solution of nickel salt and manganese salt according to stoichiometric proportion Ni: Mn=1: 1, in described mixed solution, add the precipitation reagent of excessive 2 ~ 6%, obtain nickel manganese compound carbonate precipitation or nickel-manganese composite hydroxide precipitation;
(2) LiNi is prepared with the compound of lithium and described nickel manganese compound carbonate or described nickel-manganese composite hydroxide
0.5mn
0.5o
2material.
Preferably, the described nickel salt in described step (1) is one or more in nickel nitrate, nickel acetate, nickelous sulfate, nickel chloride.
Preferably, the described manganese salt in described step (1) is one or more in manganese nitrate, manganese acetate, manganese sulfate, manganese chloride.
Preferably, the described precipitation reagent in described step (1) is any one in sodium carbonate liquor, solution of potassium carbonate, sodium hydroxide solution, potassium hydroxide solution.
Preferably, the nickel ion in the mixed solution of the described nickel salt in described step (1) and described manganese salt and the concentration of manganese ion and be 0.05 ~ 2M, the concentration of described precipitation reagent is 0.05 ~ 1M.
Preferably, stir 0.5 ~ 10 hour after adding described precipitation reagent in described step (1).
Preferably, the compound of the described lithium in described step (2) is one or more in lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, lithia.
Preferably, the compound of lithium described in described step (2) and described nickel manganese compound carbonate or described nickel-manganese composite hydroxide according to the molal quantity and nickel and manganese of getting lithium molal quantity and ratio be Li:(Ni+Mn)=(1.02 ~ 1.06): the ratio of 1 is to prepare LiNi
0.5mn
0.5o
2material.
Preferably, calcination after being mixed with described nickel manganese compound carbonate by the compound of described lithium in described step (2), obtains LiNi
0.5mn
0.5o
2material;
Or, by after described nickel manganese compound carbonate or nickel-manganese composite hydroxide calcination in described step (2), then with the compound of described lithium after calcination obtain LiNi
0.5mn
0.5o
2material.
Preferably, in described step (2), by the compound of described lithium and described nickel manganese compound carbonate or described nickel-manganese composite hydroxide according to the molal quantity getting lithium and nickel and manganese molal quantity and ratio be Li:(Ni+Mn)=(1.02 ~ 1.06): the ratio of 1 mixes, then be warmed up to 400 ~ 600 DEG C with the programming rate of 0.1 ~ 10 DEG C/min, be incubated 2 ~ 12 hours; Be warmed up to 800 ~ 950 DEG C with the programming rate of 0.1 ~ 10 DEG C/min again, calcine 2 ~ 24 hours; Cool to room temperature again, obtain LiNi
0.5mn
0.5o
2material.
Preferably, in described step (2), described nickel manganese compound carbonate or described nickel-manganese composite hydroxide are warmed up to 400 ~ 600 DEG C with the programming rate of 0.1 ~ 10 DEG C/min, are incubated 2 ~ 12 hours, obtain nickel manganese composite oxide; Then by the compound of lithium and nickel manganese composite oxide according to the molal quantity getting lithium and nickel and manganese molal quantity and ratio be Li:(Ni+Mn)=(1.02 ~ 1.06): the ratio of 1 mixes, be warmed up to 800 ~ 950 DEG C with the programming rate of 0.1 ~ 10 DEG C/min again, calcine 2 ~ 24 hours; Cool to room temperature again, obtain LiNi
0.5mn
0.5o
2material.
The present invention also provides a kind of LiNi
0.5mn
0.5o
2material, it is prepared by above-mentioned preparation method.
The present invention also provides a kind of lithium ion battery, and its positive pole contains above-mentioned material, even if prepare the positive pole of lithium ion battery by above-mentioned lithium nickel manganese oxide material, then is assembled into lithium ion battery.
Beneficial effect of the present invention: this preparation method's operating procedure is simple, coprecipitation process does not need to control the pH value in course of reaction, thus makes coprecipitation process be very easy to control, and the method is applicable to industrialization large-scale production.By the LiNi that the method prepares
0.5mn
0.5o
2cation mixing in the crystal structure of material reduces, thus substantially increases the chemical property of lithium ion in charge and discharge process.And by this LiNi
0.5mn
0.5o
2the lithium ion battery that material obtains has good cycle performance and high rate performance.
Accompanying drawing explanation
Fig. 1 is LiNi prepared by the embodiment of the present invention 1
0.5mn
0.5o
2the crystal structure figure of material;
Fig. 2 is LiNi prepared by the embodiment of the present invention 1
0.5mn
0.5o
2the XRD figure of material;
Fig. 3 is LiNi prepared by the embodiment of the present invention 1
0.5mn
0.5o
2the charge-discharge performance resolution chart of the lithium ion battery that material is made;
Fig. 4 is LiNi prepared by the embodiment of the present invention 1
0.5mn
0.5o
2the high rate performance resolution chart of the lithium ion battery that material is made;
Fig. 5 is the LiNi of comparative example 1 of the present invention preparation
0.5mn
0.5o
2the charge-discharge performance resolution chart of the lithium ion battery made of material;
Fig. 6 is the LiNi of comparative example 2 of the present invention preparation
0.5mn
0.5o
2the high rate performance resolution chart of the lithium ion battery made of material.
Embodiment
For making those skilled in the art understand technical scheme of the present invention better, below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Embodiment 1
The present embodiment provides a kind of LiNi
0.5mn
0.5o
2the preparation method of material, comprises the following steps:
(1) nickel acetate and manganese nitrate are configured mixed solution according to stoichiometric proportion Ni: Mn=1: 1, in mixed solution nickel ion and manganese ion concentration and be 0.05M.Under stirring, in described mixed solution, add the sodium hydroxide solution of 0.08M, and NaOH excessive 3% is to ensure Ni
2+, Mn
2+ion precipitation is complete, stirs after 7 hours, then leaves standstill 5 hours, centrifuge washing 3 times, and drying 8 hours at 110 DEG C, obtains nickel-manganese composite hydroxide precipitation;
(2) according to the molal quantity and nickel and manganese of getting lithium molal quantity and ratio be Li:(Ni+Mn) ratio of=1.04:1 takes lithium carbonate and nickel-manganese composite hydroxide respectively, then join in planetary ball mill, add a certain amount of ethanol again, ethanol is 1mL/g with the ratio of the amount of solid mixture, with the rotating speed ball milling 2h of 300r/min, ball milling is even.From ball mill, take out the mixture of lithium carbonate and nickel-manganese composite hydroxide, after abundant drying, then sintered in air atmosphere by temperature programmed control, be heated to 600 DEG C with the programming rate of 0.1 DEG C/min, insulation 2h; 950 DEG C are heated to again, calcining 24h with the programming rate of 10 DEG C/min; Last Temperature fall, to room temperature, namely obtains stratiform LiNi
0.5mn
0.5o
2material.
LiNi
0.5mn
0.5o
2material is that one has α-NaFeO
2the stratified material of structure, belongs to R-3m space group.As shown in Figure 1, Li occupies the 3a(0 of R-3m space group, 0,0) position, Ni and Mn takes up space the 3b(0 of group jointly, 0,0.5) position, O takes up space the 6c(0 of group, and 0, ± 0.25) position.The transition metal layer that Ni and Mn is formed jointly, this transition metal layer and lithium layer are arranged in order, separated by oxygen atom between optional intermediate metal level and lithium layer.At LiNi
0.5mn
0.5o
2crystal structure in, the average oxidation valence state of Ni and Mn is respectively+2 and+4, and in charge and discharge process, Mn is inactive, keep+4 valencys constant.Li on the 3a position of space group
+with the Ni on the 3b position of space group
2+because radius is close, easy generating portion is staggered to be occupied, and the dislocation of this crystal structure is exactly " cation mixing ".As shown in Figure 2, diffraction maximum 003 shows layered rock salt structure R3m, and diffraction maximum 104 then shows stratiform and cube rock salt structure.Dislocation phenomenon in layer structure can characterize with the intensity rate of diffraction maximum 003 with diffraction maximum 104, and their ratio is less, and cation mixing degree is larger, then can block lithium ion diffusion admittance, thus affects the chemical property of lithium ion; Their ratio is larger, then stratiform is more obvious, and mixing degree is little, the excellent electrochemical performance of lithium ion.The stratiform LiNi that the present embodiment is obtained
0.5mn
0.5o
2material product degree of crystallinity is high, without dephasign, and peak intensity I
(003)/ I
(004)ratio is comparatively large, Li
+with Ni
2+mixing degree less.
By stratiform LiNi
0.5mn
0.5o
2material, conductive agent acetylene black, binding agent PVDF(Kynoar) mix according to mass ratio 8:1:1, use NMP(1-N-methyl-2-2-pyrrolidone N-) this mixture is modulated into slurry, evenly be coated on aluminium foil, vacuumize 1h at 80 ~ 120 DEG C, obtained experimental cell pole piece.Be to electrode with lithium sheet, electrolyte is the LiPF of 1.5mol/L
6eC(ethyl carbonate ester)+DMC(dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is celgard2400 film, is assembled into CR2025 type button cell in the glove box being full of argon gas atmosphere.
As shown in Figure 3, charge and discharge cycles test is carried out to this button cell: charging/discharging voltage scope is 2.5 ~ 4.5V, be the condition of 0.1C at charging and discharging currents under, first discharge specific capacity is 196.238mAh/g, initial coulomb efficiency is 86%, 30 specific capacities that circulate are 185.662mAh/g, and capability retention is 94.6%, and cyclical stability is better.
As shown in Figure 4, high rate performance test is carried out to this button cell: charging/discharging voltage scope is 2.5 ~ 4.5V, and charging current is 0.1C, and discharging current is respectively 0.1C, 0.2C, 0.5C, 1C, each circulation 5 times.Wherein, 1C=200mA/g.High rate performance test result shows, 1C specific discharge capacity is still at more than 150mAh, and high rate performance is better.
This preparation method's operating procedure is simple, and coprecipitation process does not need to control the pH value in course of reaction, thus makes coprecipitation process be very easy to control, and the method is applicable to industrialization large-scale production.By the LiNi that the method prepares
0.5mn
0.5o
2cation mixing in the crystal structure of material reduces, thus substantially increases the chemical property of lithium ion in charge and discharge process.And by this LiNi
0.5mn
0.5o
2the lithium ion battery that material obtains has good cycle performance and high rate performance.
Comparative example 1
First the NiSO of respective quality is taken according to amount of substance than for 1:1
46H
2o and MnSO
4h
2o also mixes and is configured to the metal salt solution that concentration is 2M concentration.To calculate and the amount compound concentration taking required precipitation reagent is the solution (in the reaction system of NaOH as precipitation reagent, adding according to aqueous slkali amount the mixed solution that a certain amount of ammoniacal liquor is mixed with certain density ammoniacal liquor and NaOH in NaOH solution) of 2M concentration simultaneously.Adopt the mode of cocurrent adding material, be slowly added dropwise in reactor simultaneously, keeping the pH value of system in course of reaction constant by control charging rate is 11.Adopt paddle at the uniform velocity stirring reaction liquid, until material dropping completely after, then stir 6h and namely obtain coprecipitated product.According to amount and the LiOHH of institute's metal ion in the coprecipitated product obtained
2o, sinters after the two being mixed than being 1:1.05 according to amount of substance.Begin to warm to 850 ° of C from room temperature, and sinter 10h under 850 ° of C, obtain LiNi
0.5mn
0.5o
2material.As shown in Figure 5, according to the method preparing button cell in embodiment 1, use the LiNi that this comparative example is obtained
0.5mn
0.5o
2button cell made by material, and carries out charge and discharge cycles test to this battery: charging/discharging voltage scope 2.8 ~ 4.5V, charging and discharging currents density is 30mAg
-1condition under, first discharge specific capacity 178mAh/g, the specific capacity after 50 times that circulates is about 165mAh/g, and capability retention is 92.7%.
LiNi prepared by embodiment 1
0.5mn
0.5o
2the lithium ion battery that material is made and LiNi prepared by comparative example 1
0.5mn
0.5o
2the lithium ion battery made of material capability retention after circulation 30 times is suitable, and LiNi prepared by embodiment 1
0.5mn
0.5o
2higher than in comparative example 1 of the first discharge specific capacity of the lithium ion battery that material is made.Need the speed by controlling to add precipitation reagent to control the pH value of coprecipitation reaction in comparative example 1, the pH of reaction system is very rambunctious, substantially increases the difficulty of coprecipitation reaction process control like this.LiNi in embodiment 1
0.5mn
0.5o
2in material preparation process, coprecipitation reaction condition is more prone to control, as long as directly add the precipitation reagent of set amount, regulates the pH value of reaction system, enormously simplify the control for course of reaction, and can ensure LiNi without the need to the moment
0.5mn
0.5o
2material is the consistency of coprecipitation reaction in production process repeatedly, is particularly useful for suitability for industrialized production.
Comparative example 2
First by the LiOHH of 10mmol
2the NiNO of O and 5mmol
36H
2o is dissolved in distilled water, then adds the nano level γ-MnO of 5mmol
2, limit edged stirs, and finally forms mixture.At 120 DEG C, by the moisture evaporate to dryness in mixture.And then the mixture after evaporating water is raised to 800 DEG C from room temperature, and at 800 DEG C calcination 5h, obtain LiNi
0.5mn
0.5o
2.As shown in Figure 6, the method obtains the lithium nickel manganese oxide material of nanometer spherical.According to the method preparing button cell in embodiment 1, use the LiNi that this comparative example is obtained
0.5mn
0.5o
2button cell made by material, and carries out high rate performance to this battery: charging/discharging voltage scope 2.5 ~ 4.2V, and 1.6C specific discharge capacity is 145.3mAh/g.
LiNi prepared by embodiment 1
0.5mn
0.5o
2the lithium ion battery that material is made, high rate performance test result shows, 1C specific discharge capacity is still at more than 150mAh, and high rate performance is better.LiNi prepared by embodiment 1
0.5mn
0.5o
2lithium ion battery in the high rate performance of the lithium ion battery that material is made and comparative example 2 is suitable.And embodiment 1 obtains in the crystal structure of nickel-manganese composite hydroxide by coprecipitation, the arrangement of nickel and manganese is more even, thus makes final obtained LiNi
0.5mn
0.5o
2material has better crystal structure.And in comparative example 2, directly use LiOHH
2o, NiNO
36H
2o, γ-MnO
2directly prepare LiNi by solid phase method high temperature sintering
0.5mn
0.5o
2material, because solid phase reaction is difficult to nickel and manganese to be uniformly dispersed, so the arrangement of nickel and manganese is uneven in the crystal structure of obtained end product.Although use LiNi prepared by the method
0.5mn
0.5o
2lithium ion battery prepared by material has excellent high rate performance, but LiNi
0.5mn
0.5o
2the crystal structure of material is not good.
Embodiment 2
The present embodiment provides a kind of LiNi
0.5mn
0.5o
2the preparation method of material, comprises the following steps:
(1) by the mixture (wherein, the mol ratio of manganese chloride and manganese acetate is 1:1) of nickelous sulfate and manganese chloride and manganese acetate according to stoichiometric proportion Ni: Mn=1: 1 to configure mixed solution, in mixed solution nickel ion and manganese ion concentration and be 1.5M.Under stirring, in described mixed solution, add the solution of potassium carbonate of 0.05M, and potash excessive 2% is to ensure Ni
2+, Mn
2+ion precipitation is complete, stirs after 0.5 hour, then leaves standstill 3 hours, centrifuge washing 3 times, and drying 4 hours at 110 DEG C, obtains nickel manganese compound carbonate precipitation;
(2) according to the molal quantity and nickel and manganese of getting lithium molal quantity and ratio be Li:(Ni+Mn) ratio of=1.02:1 takes the mixture of lithium nitrate and lithium acetate (wherein respectively, the mol ratio of lithium nitrate and lithium acetate is 1:2) and nickel manganese compound carbonate, then join in planetary ball mill, add a certain amount of ethanol again, ethanol is 1.5mL/g with the ratio of the amount of solid mixture, with the rotating speed ball milling 6h of 500r/min, ball milling is even.The mixture of lithium nitrate and lithium acetate is taken out (wherein from ball mill, the mol ratio of lithium nitrate and lithium acetate is 1:2) and nickel manganese compound carbonate, after abundant drying, then sintered in air atmosphere by temperature programmed control, 500 DEG C are heated to, insulation 12h with the programming rate of 4 DEG C/min; 900 DEG C are heated to again, calcining 12h with the programming rate of 5 DEG C/min; Last Temperature fall, to room temperature, namely obtains stratiform LiNi
0.5mn
0.5o
2material.
According to the method preparing button cell in embodiment 1, use the LiNi that the present embodiment is obtained
0.5mn
0.5o
2button cell made by material, and carries out charge-discharge performance test to this battery: charging and discharging currents is 0.1C, and first discharge specific capacity is 189.96mAh/g, initial coulomb efficiency is 88%, 30 specific capacities that circulate are 177.613mAh/g, and capability retention is 93.5%, and cyclical stability is better.
Embodiment 3
The present embodiment provides a kind of LiNi
0.5mn
0.5o
2the preparation method of material, comprises the following steps:
(1) nickel chloride and manganese chloride are configured mixed solution according to stoichiometric proportion Ni: Mn=1: 1, in mixed solution nickel ion and manganese ion concentration and be 0.5M.Under stirring, in described mixed solution, add the sodium carbonate liquor of 0.09M, and sodium carbonate excessive 4% is to ensure Ni
2+, Mn
2+ion precipitation is complete, stirs after 3 hours, then leaves standstill 1 hour, centrifuge washing 3 times, and drying 7 hours at 110 DEG C, obtains nickel manganese compound carbonate precipitation;
(2) according to the molal quantity and nickel and manganese of getting lithium molal quantity and ratio be Li:(Ni+Mn) ratio of=1.03:1 takes lithia and nickel manganese compound carbonate respectively, then join in planetary ball mill, add a certain amount of ethanol again, ethanol is 1.3mL/g with the ratio of the amount of solid mixture, with the rotating speed ball milling 4h of 650r/min, ball milling is even.From ball mill, take out the mixture of lithia and nickel manganese compound carbonate, after abundant drying, then sintered in air atmosphere by temperature programmed control, be heated to 450 DEG C with the programming rate of 10 DEG C/min, insulation 7h; 800 DEG C are heated to again, calcining 2h with the programming rate of 0.1 DEG C/min; Last Temperature fall, to room temperature, namely obtains stratiform LiNi
0.5mn
0.5o
2material.
According to the method preparing button cell in embodiment 1, use the LiNi that the present embodiment is obtained
0.5mn
0.5o
2button cell made by material, and carries out charge-discharge performance test to this battery: charging and discharging currents is 0.1C, and first discharge specific capacity is 203.12mAh/g, initial coulomb efficiency is 90.1%, 30 specific capacities that circulate are 193.776mAh/g, and capability retention 95.4% is that cyclical stability is better.
Embodiment 4
The present embodiment provides a kind of LiNi
0.5mn
0.5o
2the preparation method of material, comprises the following steps:
(1) nickel nitrate and manganese acetate are configured mixed solution according to stoichiometric proportion Ni: Mn=1: 1, in mixed solution nickel ion and manganese ion concentration and be 1M.Under stirring, in described mixed solution, add the potassium hydroxide solution of 1M, and potassium hydroxide excessive 6% is to ensure Ni
2+, Mn
2+ion precipitation is complete, stirs after 10 hours, then leaves standstill 2 hours, centrifuge washing 3 times, and drying 10 hours at 110 DEG C, obtains nickel-manganese composite hydroxide precipitation;
(2) according to the molal quantity and nickel and manganese of getting lithium molal quantity and ratio be Li:(Ni+Mn) ratio of=1.06:1 takes lithium hydroxide and nickel-manganese composite hydroxide respectively, then join in planetary ball mill, add a certain amount of ethanol again, ethanol is 1.4mL/g with the ratio of the amount of solid mixture, with the rotating speed ball milling 10h of 450r/min, ball milling is even.From ball mill, take out the mixture of lithium hydroxide and nickel-manganese composite hydroxide, after abundant drying, then sintered in air atmosphere by temperature programmed control, be heated to 400 DEG C with the programming rate of 8 DEG C/min, insulation 10h; 850 DEG C are heated to again, calcining 18h with the programming rate of 7 DEG C/min; Last Temperature fall, to room temperature, namely obtains stratiform LiNi
0.5mn
0.5o
2material.
According to the method preparing button cell in embodiment 1, use the LiNi that the present embodiment is obtained
0.5mn
0.5o
2button cell made by material, and carries out charge-discharge performance test to this battery: charging and discharging currents is 0.1C, and first discharge specific capacity is 182.6mAh/g, initial coulomb efficiency is 87%, 30 specific capacities that circulate are 168.54mAh/g, and capability retention is 92.3%, and cyclical stability is better.
Embodiment 5
The present embodiment provides a kind of LiNi
0.5mn
0.5o
2the preparation method of material, comprises the following steps:
(1) by the mixture (wherein, the mol ratio of nickel chloride and nickelous sulfate is 1:2) of nickel chloride and nickelous sulfate with manganese sulfate according to stoichiometric proportion Ni: Mn=1: 1 to configure mixed solution, in mixed solution nickel ion and manganese ion concentration and be 2M.Under stirring, in described mixed solution, add the sodium hydroxide solution of 0.07M, and NaOH excessive 5% is to ensure Ni
2+, Mn
2+ion precipitation is complete, stirs after 5 hours, then leaves standstill 4 hours, centrifuge washing 3 times, and drying 6 hours at 110 DEG C, obtains nickel-manganese composite hydroxide precipitation;
(2) nickel-manganese composite hydroxide is warmed up to 600 DEG C with the programming rate of 2 DEG C/min, is incubated 12 hours, obtains nickel manganese composite oxide; According to the molal quantity and nickel and manganese of getting lithium molal quantity and ratio be Li:(Ni+Mn) ratio of=1.03:1 takes lithium carbonate and nickel manganese composite oxide respectively, then join in planetary ball mill, add a certain amount of ethanol again, ethanol is 1.5mL/g with the ratio of the amount of solid mixture, with the rotating speed ball milling 5h of 400r/min, ball milling is even.From ball mill, take out the mixture of lithium carbonate and nickel manganese composite oxide, after abundant drying, then sintered in air atmosphere by temperature programmed control, be heated to 950 DEG C with the programming rate of 8 DEG C/min, calcining 12h; Last Temperature fall, to room temperature, namely obtains stratiform LiNi
0.5mn
0.5o
2material.
According to the method preparing button cell in embodiment 1, use the LiNi that the present embodiment is obtained
0.5mn
0.5o
2button cell made by material, and carries out charge-discharge performance test to this battery: charging and discharging currents is 0.1C, and first discharge specific capacity is 199.56mAh/g, and 30 specific capacities that circulate are 191.978mAh/g, and capability retention is 96.2%, and cyclical stability is better.
Embodiment 6
The present embodiment provides a kind of LiNi
0.5mn
0.5o
2the preparation method of material, comprises the following steps:
(1) nickel chloride and manganese nitrate are configured mixed solution according to stoichiometric proportion Ni: Mn=1: 1, in mixed solution nickel ion and manganese ion concentration and be 1.3M.Under stirring, in described mixed solution, add the sodium carbonate liquor of 0.06M, and sodium carbonate excessive 4% is to ensure Ni
2+, Mn
2+ion precipitation is complete, stirs after 8 hours, then leaves standstill 5 hours, centrifuge washing 3 times, and drying 12 hours at 110 DEG C, obtains nickel manganese compound carbonate precipitation;
(2) nickel manganese compound carbonate is warmed up to 400 DEG C with the programming rate of 5 DEG C/min, is incubated 2 hours, obtains nickel manganese composite oxide; According to the molal quantity and nickel and manganese of getting lithium molal quantity and ratio be Li:(Ni+Mn) ratio of=1.04:1 takes lithium nitrate and nickel manganese composite oxide respectively, then join in planetary ball mill, add a certain amount of ethanol again, ethanol is 1.2mL/g with the ratio of the amount of solid mixture, with the rotating speed ball milling 2h of 300r/min, ball milling is even.From ball mill, take out the mixture of lithium nitrate and nickel manganese composite oxide, after abundant drying, then sintered in air atmosphere by temperature programmed control, be heated to 800 DEG C with the programming rate of 0.1 DEG C/min, calcining 2h; Last Temperature fall, to room temperature, namely obtains stratiform LiNi
0.5mn
0.5o
2material.
Embodiment 7
The present embodiment provides a kind of LiNi
0.5mn
0.5o
2the preparation method of material, comprises the following steps:
(1) nickel acetate and manganese sulfate are configured mixed solution according to stoichiometric proportion Ni: Mn=1: 1, in mixed solution nickel ion and manganese ion concentration and be 0.3M.Under stirring, in described mixed solution, add the potassium hydroxide solution of 0.05M, and potassium hydroxide excessive 5% is to ensure Ni
2+, Mn
2+ion precipitation is complete, stirs after 6 hours, then leaves standstill 1 hour, centrifuge washing 3 times, and drying 5 hours at 110 DEG C, obtains nickel-manganese composite hydroxide precipitation;
(2) nickel-manganese composite hydroxide is warmed up to 550 DEG C with the programming rate of 0.1 DEG C/min, is incubated 4 hours, obtains nickel manganese composite oxide; According to the molal quantity and nickel and manganese of getting lithium molal quantity and ratio be Li:(Ni+Mn) ratio of=1.02:1 takes the mixture of lithium hydroxide and lithia (wherein respectively, the mol ratio of lithium hydroxide and lithia is 3:1) and nickel manganese composite oxide, then join in planetary ball mill, add a certain amount of ethanol again, ethanol is 1mL/g with the ratio of the amount of solid mixture, with the rotating speed ball milling 7h of 500r/min, ball milling is even.The mixture of lithium hydroxide and lithia is taken out (wherein from ball mill, the mol ratio of lithium hydroxide and lithia is 3:1) and nickel manganese composite oxide, after abundant drying, then sintered in air atmosphere by temperature programmed control, 850 DEG C are heated to, calcining 14h with the programming rate of 5 DEG C/min; Last Temperature fall, to room temperature, namely obtains stratiform LiNi
0.5mn
0.5o
2material.
Embodiment 8
The present embodiment provides a kind of LiNi
0.5mn
0.5o
2the preparation method of material, comprises the following steps:
(1) nickelous sulfate and manganese chloride are configured mixed solution according to stoichiometric proportion Ni: Mn=1: 1, in mixed solution nickel ion and manganese ion concentration and be 1.6M.Under stirring, in described mixed solution, add the solution of potassium carbonate of 1M, and potash excessive 2% is to ensure Ni
2+, Mn
2+ion precipitation is complete, stirs after 4 hours, then leaves standstill 2 hours, centrifuge washing 3 times, and drying 11 hours at 110 DEG C, obtains nickel manganese compound carbonate precipitation;
(2) nickel manganese compound carbonate is warmed up to 500 DEG C with the programming rate of 10 DEG C/min, is incubated 7 hours, obtains nickel manganese composite oxide; According to the molal quantity and nickel and manganese of getting lithium molal quantity and ratio be Li:(Ni+Mn) ratio of=1.06:1 takes lithium acetate and nickel manganese composite oxide respectively, then join in planetary ball mill, add a certain amount of ethanol again, ethanol is 1.3mL/g with the ratio of the amount of solid mixture, with the rotating speed ball milling 10h of 650r/min, ball milling is even.From ball mill, take out the mixture of lithium acetate and nickel manganese composite oxide, after abundant drying, then sintered in air atmosphere by temperature programmed control, be heated to 900 DEG C with the programming rate of 10 DEG C/min, calcining 24h; Last Temperature fall, to room temperature, namely obtains stratiform LiNi
0.5mn
0.5o
2material.
Embodiment 9
The present embodiment provides a kind of LiNi
0.5mn
0.5o
2the preparation method of material, it is prepared by above-mentioned method.
Embodiment 10
The present embodiment provides a kind of lithium ion battery, and its positive pole contains above-mentioned LiNi
0.5mn
0.5o
2material.
Certainly, other known material, the element etc. such as negative material, collector should also be comprised in the lithium ion battery of this enforcement.
Be understandable that, the illustrative embodiments that above execution mode is only used to principle of the present invention is described and adopts, but the present invention is not limited thereto.For those skilled in the art, without departing from the spirit and substance in the present invention, can make various modification and improvement, these modification and improvement are also considered as protection scope of the present invention.
Claims (5)
1. a LiNi
0.5mn
0.5o
2the preparation method of material, is characterized in that, comprises the following steps:
(1) nickel salt and manganese salt are configured the mixed solution of nickel salt and manganese salt according to stoichiometric proportion Ni: Mn=1: 1, the precipitation reagent of excessive 2 ~ 6% molal quantitys is added in described mixed solution, obtain nickel manganese compound carbonate precipitation or nickel-manganese composite hydroxide precipitation, wherein, described precipitation reagent is any one in sodium carbonate liquor, solution of potassium carbonate, sodium hydroxide solution, potassium hydroxide solution, and the concentration of described precipitation reagent is 0.05 ~ 1M;
(2) LiNi is prepared with the compound of lithium and described nickel manganese compound carbonate or described nickel-manganese composite hydroxide
0.5mn
0.5o
2material,
Wherein, in described step (2), by the compound of described lithium and described nickel manganese compound carbonate or described nickel-manganese composite hydroxide according to the molal quantity getting lithium and nickel and manganese molal quantity and ratio be Li:(Ni+Mn)=(1.02 ~ 1.06): the ratio of 1 mixes, then be warmed up to 400 ~ 600 DEG C with the programming rate of 0.1 ~ 10 DEG C/min, be incubated 2 ~ 12 hours; Be warmed up to 800 ~ 950 DEG C with the programming rate of 0.1 ~ 10 DEG C/min again, calcine 2 ~ 24 hours; Cool to room temperature again, obtain LiNi
0.5mn
0.5o
2material;
Or, in described step (2), described nickel manganese compound carbonate or described nickel-manganese composite hydroxide are warmed up to 400 ~ 600 DEG C with the programming rate of 0.1 ~ 10 DEG C/min, are incubated 2 ~ 12 hours, obtain nickel manganese composite oxide; Then by the compound of lithium and nickel manganese composite oxide according to the molal quantity getting lithium and nickel and manganese molal quantity and ratio be Li:(Ni+Mn)=(1.02 ~ 1.06): the ratio of 1 mixes, be warmed up to 800 ~ 950 DEG C with the programming rate of 0.1 ~ 10 DEG C/min again, calcine 2 ~ 24 hours; Cool to room temperature again, obtain LiNi
0.5mn
0.5o
2material;
Described LiNi
0.5mn
0.5o
2material is stratified material, without dephasign.
2. LiNi according to claim 1
0.5mn
0.5o
2the preparation method of material, is characterized in that, the described nickel salt in described step (1) is one or more in nickel nitrate, nickel acetate, nickelous sulfate, nickel chloride.
3. LiNi according to claim 1
0.5mn
0.5o
2the preparation method of material, is characterized in that, the described manganese salt in described step (1) is one or more in manganese nitrate, manganese acetate, manganese sulfate, manganese chloride.
4. LiNi according to claim 1
0.5mn
0.5o
2the preparation method of material, is characterized in that, the nickel ion in the mixed solution of the described nickel salt in described step (1) and described manganese salt and the concentration of manganese ion and be 0.05 ~ 2M.
5. LiNi according to claim 1
0.5mn
0.5o
2the preparation method of material, is characterized in that, the compound of the described lithium in described step (2) is one or more in lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, lithia.
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| JP6583418B2 (en) * | 2015-08-24 | 2019-10-02 | 住友金属鉱山株式会社 | Manganese nickel composite hydroxide and method for producing the same, lithium manganese nickel composite oxide and method for producing the same, and non-aqueous electrolyte secondary battery |
| CN105261752B (en) * | 2015-11-18 | 2018-02-06 | 哈尔滨工业大学 | A kind of preparation method of high pressure nickel lithium manganate cathode material |
| US11952287B2 (en) | 2016-07-20 | 2024-04-09 | Haldor Topsøe A/S | Method for the precipitation of particles of a metal carbonate material without use of a chelating agent |
| CN108083342B (en) * | 2017-10-31 | 2019-08-13 | 湖南海利锂电科技股份有限公司 | Lithium-ion-power cell manganate cathode material for lithium and preparation method thereof |
| WO2020218475A1 (en) * | 2019-04-26 | 2020-10-29 | パナソニックＩｐマネジメント株式会社 | Positive electrode active material for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery |
| CN111916697B (en) * | 2020-07-14 | 2021-09-21 | 蜂巢能源科技有限公司 | Cobalt-free cathode material, preparation method thereof, lithium ion battery cathode and lithium battery |
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