CN103474647A - Preparation method of modified spinel lithium manganese oxide cathode material - Google Patents
Preparation method of modified spinel lithium manganese oxide cathode material Download PDFInfo
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- CN103474647A CN103474647A CN2013104123595A CN201310412359A CN103474647A CN 103474647 A CN103474647 A CN 103474647A CN 2013104123595 A CN2013104123595 A CN 2013104123595A CN 201310412359 A CN201310412359 A CN 201310412359A CN 103474647 A CN103474647 A CN 103474647A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000010406 cathode material Substances 0.000 title claims abstract description 14
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 7
- 239000011029 spinel Substances 0.000 title claims abstract description 7
- 229910002102 lithium manganese oxide Inorganic materials 0.000 title abstract 3
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 title abstract 3
- 238000005245 sintering Methods 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 40
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000011572 manganese Substances 0.000 claims abstract description 21
- 239000003513 alkali Substances 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 18
- 238000004381 surface treatment Methods 0.000 claims abstract description 13
- 239000002019 doping agent Substances 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- 229910052796 boron Inorganic materials 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 19
- 230000014759 maintenance of location Effects 0.000 claims description 12
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 claims description 11
- 238000009413 insulation Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000007873 sieving Methods 0.000 abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract 2
- 101100347614 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) MYO4 gene Proteins 0.000 abstract 1
- 150000004679 hydroxides Chemical class 0.000 abstract 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 abstract 1
- 229910052808 lithium carbonate Inorganic materials 0.000 abstract 1
- 150000002642 lithium compounds Chemical class 0.000 abstract 1
- 150000002697 manganese compounds Chemical class 0.000 abstract 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 abstract 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 abstract 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 abstract 1
- 239000003607 modifier Substances 0.000 abstract 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000243 solution Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 150000002696 manganese Chemical class 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- 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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Abstract
The invention discloses a preparation method of modified spinel lithium manganese oxide, an cathode material for a lithium ion cell. The preparation method comprises the following steps of metering one or more than two manganese compounds selected from MnO2, Mn3O4, Mn(OH)2 and Mn2O3, a lithium compound selected from Li2CO3 and LiOH and one or more doping agents selected from oxides or hydroxides of Cr, La, Ce, Zr, Ni, Mg, Ti, Al, Ca, V and B according to a chemical formula Li(1+X)Mn(2-X-Y)MYO4 (M is a doping modifier, X is not less than 0 and not more than 0.20 and Y is not less than 0 and not more than 0.25), mixing the materials uniformly, then carrying out sintering and surface treatment, reducing the alkali content of the sintered substance through surface treatment, controlling the alkali content in a certain range and then carrying out smashing, dispersing and grading and sieving, thus obtaining the uniformly doped lithium manganese oxide cathode material. The method is simple, the preparation processes are easy to operate and control, the production cost is low and the product performances are excellent.
Description
Technical field
The present invention relates to a kind of method for preparing anode material of lithium-ion battery, say more specifically a kind of preparation method of modified spinelle type manganate cathode material for lithium.
Background technology
Lithium manganate having spinel structure has advantages of aboundresources, cheap, nontoxic pollution-free, in recent years by extensive concern, and the LiMn2O4 application is very extensive, LiMn2O4 is as the positive electrode of lithium ion battery, be mainly used in the following aspects: (1) portable electric appts, as notebook computer, video camera, camera, game machine, small-sized Medical Devices etc.; (2) communication equipment, as mobile phone, cordless telephone, satellite communication, intercom etc.; (3) military equipment, as guided missile ignition system, artillery transmitter, submarine, torpedo and military use that some are special; (4) transit equipment, as electric automobile, motorcycle, bicycle, Small Leisure car etc.But existing lithium manganate material ubiquity cycle performance is not good enough and the poor shortcoming of high-temperature behavior.Therefore, cycle performance and the high-temperature stability of raising LiMn2O4 are the improved directions of current lithium manganate material.
Summary of the invention
Goal of the invention: the present invention, in order to solve the deficiencies in the prior art, provides a kind of preparation method of modified spinelle type LiMn2O4 of high low temperature good cycle.
Technical scheme: a kind of preparation method of modified spinelle type manganate cathode material for lithium comprises the steps:
(1) by manganese source substance, lithium source substance, dopant according to chemical formula Li
(1+X)mn
(2-X-Y)m
yo
4carry out batching, wherein M is the doping vario-property agent, and 0≤X≤0.20,0≤Y≤0.25, in dry-mixed machine or batch mixer, mixes 10-60min;
(2) material in step (1) is put into to crucible pushes Muffle furnace or kiln carries out sintering, sintering temperature is controlled at 650～1150 ℃, temperature retention time is 4～50h, cool to again 500～1000 ℃, insulation 1～15h, finally be cooled to room temperature, whole sintering process is to carry out under air or oxygen atmosphere, and the throughput control range is 0.6～4m
3/ h;
(3) if also need the above sintering of secondary, the material that step (2) is obtained carries out the above sintering of secondary, the above sintering temperature of secondary is controlled at 550～1050 ℃, temperature retention time is 2～30h, cool to again 450～1000 ℃, be incubated 1～15h, finally be cooled to room temperature, whole sintering process is to carry out under air or oxygen atmosphere, and the throughput control range is 0.5～4m
3/ h;
(4) material step (2) or (3) obtained carries out surface treatment to reduce alkali content, and the reduction scope of alkali content must be controlled LiOH≤0.01%, Li
2cO
3≤ 0.05%, be quality percentage;
(5) material classification step (4) obtained is sieved, and obtains the lithium manganate having spinel structure material of modification.
As preferably, manganese source substance is selected from as MnO
2, Mn
3o
4, Mn (OH)
2, Mn
2o
3a kind of or two or more, D50 is between 2～20 microns.
As preferably, lithium source substance is selected from as Li
2cO
3perhaps LiOH.
As preferably, dopant is selected from as the oxide of Cr, La, Ce, Zr, Ni, Mg, Ti, Al, Ca, V, B or one or more of hydroxide.
As preferably, step (2) and (3) sintering number are for once or more than secondary.
As preferably, reduce the method for alkali content in step (4) for washing, surface coats, and improves sintering temperature, increases sintering number, and the increase throughput, extend sintering time.
Beneficial effect: the prepared product of this method is even particle size distribution not only, and D50 is 4～30 μ m, can require to carry out adjustment in various degree; And improved circulation and the high-temperature behavior of battery, and high rate performance is good.Processing step of the present invention is simple, and cost is low, is easy to realize large-scale industrial production.Specifically have the following advantages: (1) the present invention takes solid-phase synthesis, and production process is simple and easy to control; (2) the present invention adopts not equality of temperature section to control sintering process, promotes that crystal growth is even; (3) by doping and surface treatment, play modification and modification, can obtain premium quality product, specific capacity improves, and high rate performance and cycle performance are good, the high-temperature behavior excellence.The method technique is simple, and production cost is low, and production process is easy to control and operation, is easy to large-scale industrial production, and can solve the fast problem of capacity attenuation that LiMn2O4 exists in storage or discharge cycles process.
The accompanying drawing explanation
The XRD figure that Fig. 1 is the synthetic LiMn2O4 powder of embodiment 1;
The SEM figure that Fig. 2 is the synthetic LiMn2O4 powder of embodiment 1;
The first charge-discharge specific capacity curve chart that Fig. 3 is the synthetic LiMn2O4 powder of embodiment 1;
25 ℃ of cyclic curve figure that Fig. 4 is the synthetic LiMn2O4 powder of embodiment 1.
Embodiment
The present invention will now be further detailed embodiment:
Embodiment 1
(1) under the wet method environment, by concentration is 0.5～3mol/L manganese salt solution, concentration is 1～10mol/L NaOH solution and the enveloping agent solution of 0.5～200g/L, add together in reaction vessel, control suitable temperature, pH value and stirring condition, obtain the Mn of desired particle size
3o
4;
(2) Mn obtained with above-mentioned reaction
3o
4(3 μ m), LiOH and MgO be as raw material, according to the mol ratio of Li:Mn:M, is that 1.10:1.75:0.15 is prepared burden, and puts into dry-mixed machine mixing 30min, the powder that obtains mixing;
(3) material after mixing is put into after crucible and pushed Muffle furnace and carry out once sinteredly, at first temperature is controlled at 750 ℃, insulation 6h, and then cooling to 600 ℃, insulation 4h, finally be cooled to room temperature, the gas that the sintering overall process passes into is air, and the control throughput is 1.5m
3/ h;
(4) material step (3) obtained carries out surface treatment to reduce alkali content, and in the present embodiment, surface treatment is washing, and the reduction scope of alkali content must be controlled LiOH≤0.01%, Li
2cO
3≤ 0.05%, be quality percentage; Battery high rate performance, normal temperature or high temperature cyclic performance that alkali content is controlled in this scope are good, (LiOH>=0.01%, Li when alkali content is high
2cO
3>=0.05%, be quality percentage), the carbon dioxide of generation is to reacting unfavorable.Material after washing is dry 8h at a certain temperature;
(5) disperse dried material is broken, then, through the classification processing of sieving, obtain required LiMn2O4 material.
The chemical property of above-mentioned material is tested by the following method: with embodiment 1, synthetic LiMn2O4 is positive active material, and the lithium sheet is negative pole, is assembled into experimental button cell.Cathode film consist of m
(active material): m
(acetylene black): m
(PVDF)=90: 5: 5, adopt blue electricity to be tested, charging/discharging voltage is 3～4.3V, charge-discharge magnification is 0.2C.Now the specific discharge capacity of battery can reach 104.6mAh/g, under battery normal temperature the circulation 100 times after, capability retention is greater than 97.5%.
As shown in Figure 1, phase is very pure as can be seen from Figure 1, better crystallinity degree for the XRD of the sample of the present embodiment; As shown in Figure 2, as can be seen from Figure 2, even particle distribution, be regular spinelle shape to appearance structure figure; The first charge-discharge curve as shown in Figure 3; As shown in Figure 4, as can be seen from Figure 4, the product cycle performance of present case is good for the normal temperature cyclic curve.
Embodiment 2
(1) under the wet method environment, by concentration is 0.5～3mol/L manganese salt solution, concentration is 1～10mol/L NaOH solution and the enveloping agent solution of 0.5～200g/L, add together in reaction vessel, control suitable temperature, pH value and stirring condition, obtain the Mn of desired particle size
3o
4;
(2) select Mn
3o
4(3 μ m), LiOH and ZrO
2as raw material, according to the mol ratio of Li:Mn:M, be that 1.10:1.80:0.10 is prepared burden, put into dry-mixed machine mixing 30min, the powder that obtains mixing;
(3) material after mixing is put into after crucible and pushed Muffle furnace and carry out once sinteredly, at first temperature is controlled at 770 ℃, insulation 7h, and then cooling to 650 ℃, insulation 3h, finally be cooled to room temperature, the gas that the sintering overall process passes into is air, and the control throughput is 1.5m
3/ h;
(4) material of step (3) is put into again to crucible and pushed Muffle furnace and carry out double sintering, at first sintering temperature is controlled at 680 ℃, sintering 4h, then be cooled to 580 ℃ of sintering 3h, finally be cooled to room temperature, the gas that the sintering overall process passes into is air, and the control throughput is 1.3m
3/ h;
(5) material step (4) obtained carries out surface treatment to reduce alkali content, and in the present embodiment, surface treatment is washing, and the reduction scope of alkali content must be controlled LiOH≤0.01%, Li
2cO
3≤ 0.05%, be quality percentage; Battery high rate performance, normal temperature or high temperature cyclic performance that alkali content is controlled in this scope are good, (LiOH>=0.01%, Li when alkali content is high
2cO
3>=0.05%, be quality percentage), the carbon dioxide of generation is to reacting unfavorable.Material after washing is dry 8h at a certain temperature;
(6) by the broken dispersion of the material of step (5), the more classified processing of sieving, required LiMn2O4 material obtained.
The chemical property of above-mentioned material is tested by the following method: with embodiment 2, synthetic LiMn2O4 is positive active material, and the lithium sheet is negative pole, is assembled into experimental button cell.Cathode film consist of m
(active material): m
(acetylene black): m
(PVDF)=90: 5: 5, adopt blue electricity to be tested, charging/discharging voltage is 3～4.3V, charge-discharge magnification is 0.2C.Now the specific discharge capacity of battery can reach 101.1mAh/g, under battery normal temperature the circulation 100 times after, capability retention is greater than 96.5%.
Embodiment 3:
A kind of preparation method of modified spinelle type manganate cathode material for lithium, comprise the steps:
(1) under the wet method environment, by concentration is 0.5～3mol/L manganese salt solution, concentration is 1～10mol/L NaOH solution and the enveloping agent solution of 0.5～200g/L, add together in reaction vessel, control suitable temperature, pH value and stirring condition, obtain the Mn of desired particle size
3o
4;
(2) select Mn
3o
4(3 μ m), LiOH and NiO are as raw material, according to chemical formula Li
(1+X)mn
(2-X-Y)m
yo
4carry out batching, wherein M is the doping vario-property agent, and X is that 0.20, Y is 0.25, in dry-mixed machine or batch mixer, mixes 10min;
(3) material in step (2) is put into to crucible pushes Muffle furnace or kiln carries out sintering, sintering temperature is controlled at 650 ℃, temperature retention time is 4h, cool to again 500 ℃, insulation 1h, finally be cooled to room temperature, whole sintering process is to carry out under the oxygen atmosphere, and the throughput control range is 0.6m
3/ h;
(4) material step (3) obtained carries out double sintering, and the double sintering temperature is controlled at 550 ℃, and temperature retention time is 2h, cool to 450 ℃, insulation 1h, finally be cooled to room temperature again, whole sintering process is to carry out under the oxygen atmosphere, and the throughput control range is 0.5m
3/ h;
(5) material step (4) obtained carries out surface treatment to reduce alkali content, and in the present embodiment, surface treatment is washing, and the reduction scope of alkali content must be controlled LiOH≤0.01%, Li
2cO
3≤ 0.05%, be quality percentage, the material after washing is dry 6h at a certain temperature;
(6) material that step (5) obtained is broken disperse after, the more classified processing of sieving, obtain the lithium manganate having spinel structure material of modification.
The chemical property of above-mentioned material is tested by the following method: with embodiment 3, synthetic LiMn2O4 is positive active material, and the lithium sheet is negative pole, is assembled into experimental button cell.Cathode film consist of m
(active material): m
(acetylene black): m
(PVDF)=90: 5: 5, adopt blue electricity to be tested, charging/discharging voltage is 3～4.3V, charge-discharge magnification is 0.2C.Now the specific discharge capacity of battery can reach 104.9mAh/g, under battery normal temperature the circulation 100 times after, capability retention is greater than 95.8%.
Embodiment 4:
A kind of preparation method of modified spinelle type manganate cathode material for lithium, comprise the steps:
(1) under the wet method environment, by concentration is 0.5～3mol/L manganese salt solution, concentration is 1～10mol/L NaOH solution and the enveloping agent solution of 0.5～200g/L, add together in reaction vessel, control suitable temperature, pH value and stirring condition, obtain the Mn of desired particle size
3o
4;
(2) select Mn
3o
4(3 μ m), LiOH and TiO are as raw material, according to chemical formula Li
(1+X)mn
(2-X-Y)m
yo
4carry out batching, wherein M is the doping vario-property agent, and X is that 0.1, Y is 0.15, in dry-mixed machine or batch mixer, mixes 60min;
(3) material in step (2) is put into to crucible pushes Muffle furnace or kiln carries out sintering, sintering temperature is controlled at 1150 ℃, temperature retention time is 50h, cool to again 1000 ℃, insulation 15h, finally be cooled to room temperature, whole sintering process is to carry out under air atmosphere, and the throughput control range is 4m
3/ h;
(4) material step (3) obtained carries out double sintering, and the double sintering temperature is controlled at 1050 ℃, and temperature retention time is 30h, cool to 1000 ℃, insulation 15h, finally be cooled to room temperature again, whole sintering process is to carry out under air atmosphere, and the throughput control range is 4m
3/ h;
(5) material step (4) obtained carries out surface treatment to reduce alkali content, and in the present embodiment, surface treatment is that surface coats, the compound that clad material is aluminium, and the reduction scope of alkali content must be controlled LiOH≤0.01%, Li
2cO
3≤ 0.05%, be quality percentage;
(6) material that step (5) obtained is broken to be disperseed, then classification sieves, and obtains the lithium manganate having spinel structure material of modification.
The chemical property of above-mentioned material is tested by the following method: with embodiment 4, synthetic LiMn2O4 is positive active material, and the lithium sheet is negative pole, is assembled into experimental button cell.Cathode film consist of m
(active material): m
(acetylene black): m
(PVDF)=90: 5: 5, adopt blue electricity to be tested, charging/discharging voltage is 3～4.3V, charge-discharge magnification is 0.2C.Now the specific discharge capacity of battery can reach 106.1mAh/g, under battery normal temperature the circulation 100 times after, capability retention is greater than 96.0%.
Claims (6)
1. the preparation method of a modified spinelle type manganate cathode material for lithium, is characterized in that: comprise the steps:
(1) by manganese source substance, lithium source substance, dopant according to chemical formula Li
(1+X)mn
(2-X-Y)m
yo
4carry out batching, wherein M is the doping vario-property agent, and 0≤X≤0.20,0≤Y≤0.25, in dry-mixed machine or batch mixer, mixes 10-60min;
(2) material in step (1) is put into to crucible pushes Muffle furnace or kiln carries out sintering, sintering temperature is controlled at 650～1150 ℃, temperature retention time is 4～50h, cool to again 500～1000 ℃, insulation 1～15h, finally be cooled to room temperature, whole sintering process is to carry out under air or oxygen atmosphere, and the throughput control range is 0.6～4m
3/ h;
(3) if also need the above sintering of secondary, the material that step (2) is obtained carries out the above sintering of secondary, the above sintering temperature of secondary is controlled at 550～1050 ℃, temperature retention time is 2～30h, cool to again 450～1000 ℃, be incubated 1～15h, finally be cooled to room temperature, whole sintering process is to carry out under air or oxygen atmosphere, and the throughput control range is 0.5～4m
3/ h;
(4) material step (2) or (3) obtained carries out surface treatment to reduce alkali content, and the reduction scope of alkali content must be controlled LiOH≤0.01%, Li
2cO
3≤ 0.05%, be quality percentage;
(5) material classification step (4) obtained is sieved, and obtains the lithium manganate having spinel structure material of modification.
2. the preparation method of modified spinelle type manganate cathode material for lithium as claimed in claim 1, it is characterized in that: manganese source substance is selected from as MnO
2, Mn
3o
4, Mn (OH)
2, Mn
2o
3a kind of or two or more, D50 is between 2～20 microns.
3. the preparation method of modified spinelle type manganate cathode material for lithium as claimed in claim 1, it is characterized in that: lithium source substance is selected from as Li
2cO
3perhaps LiOH.
4. the preparation method of modified spinelle type manganate cathode material for lithium as claimed in claim 1, it is characterized in that: dopant is selected from as the oxide of Cr, La, Ce, Zr, Ni, Mg, Ti, Al, Ca, V, B or one or more of hydroxide.
5. the preparation method of modified spinelle type manganate cathode material for lithium as claimed in claim 1 is characterized in that: step (2) sintering number is for once, step (2) and more than (3) sintering number secondary.
6. the preparation method of modified spinelle type manganate cathode material for lithium as claimed in claim 1, it is characterized in that: the reduction method of step (4) alkali content has washing, and surface coats, improve sintering temperature, increase sintering number, increase throughput, extend sintering time.
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| CN201310412359.5A CN103474647B (en) | 2013-09-12 | 2013-09-12 | The preparation method of modified spinelle type manganate cathode material for lithium |
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| CN201310412359.5A CN103474647B (en) | 2013-09-12 | 2013-09-12 | The preparation method of modified spinelle type manganate cathode material for lithium |
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| CN103700841A (en) * | 2014-01-18 | 2014-04-02 | 南通瑞翔新材料有限公司 | High-property lithium manganate gradient anode material and preparation method thereof |
| CN103730652A (en) * | 2013-12-27 | 2014-04-16 | 广西科技大学 | Lithium battery, lithium battery cathode material and preparation method of lithium battery cathode material |
| CN104701534A (en) * | 2015-03-31 | 2015-06-10 | 南通瑞翔新材料有限公司 | High-energy-density Ni-Co-based lithium ion positive electrode material and preparation method thereof |
| CN104752714A (en) * | 2015-03-31 | 2015-07-01 | 南通瑞翔新材料有限公司 | High-capacity nickel-cobalt-based lithium ion positive electrode material and preparation method thereof |
| CN107364901A (en) * | 2017-07-27 | 2017-11-21 | 湖南长远锂科有限公司 | A kind of high-voltage spinel nickel lithium manganate cathode material and preparation method thereof |
| CN107681134A (en) * | 2017-09-07 | 2018-02-09 | 浙江瓦力新能源科技有限公司 | The preparation method of High-performance lithium manganate anode material |
| CN108539250A (en) * | 2018-03-30 | 2018-09-14 | 武汉艾特米克超能新材料科技有限公司 | A kind of solid lithium battery and preparation method thereof |
| CN109360988A (en) * | 2018-10-31 | 2019-02-19 | 云南民族大学 | A kind of nickel co-doped manganate cathode material for lithium preparation method of long-life high magnification aluminium |
| WO2020083068A1 (en) * | 2018-10-23 | 2020-04-30 | 宁德时代新能源科技股份有限公司 | Positive electrode sheet, manufacturing method therefor, lithium ion secondary battery, battery module, battery pack, and device |
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| CN103730652A (en) * | 2013-12-27 | 2014-04-16 | 广西科技大学 | Lithium battery, lithium battery cathode material and preparation method of lithium battery cathode material |
| CN103700841A (en) * | 2014-01-18 | 2014-04-02 | 南通瑞翔新材料有限公司 | High-property lithium manganate gradient anode material and preparation method thereof |
| CN103700841B (en) * | 2014-01-18 | 2017-01-18 | 南通瑞翔新材料有限公司 | Preparation method of high-property lithium manganate gradient anode material |
| CN104701534A (en) * | 2015-03-31 | 2015-06-10 | 南通瑞翔新材料有限公司 | High-energy-density Ni-Co-based lithium ion positive electrode material and preparation method thereof |
| CN104752714A (en) * | 2015-03-31 | 2015-07-01 | 南通瑞翔新材料有限公司 | High-capacity nickel-cobalt-based lithium ion positive electrode material and preparation method thereof |
| WO2016155313A1 (en) * | 2015-03-31 | 2016-10-06 | 南通瑞翔新材料有限公司 | High-capacity nickel-cobalt-based lithium ion positive electrode material and preparation method therefor |
| CN107364901A (en) * | 2017-07-27 | 2017-11-21 | 湖南长远锂科有限公司 | A kind of high-voltage spinel nickel lithium manganate cathode material and preparation method thereof |
| CN107364901B (en) * | 2017-07-27 | 2019-03-05 | 湖南长远锂科有限公司 | A kind of high-voltage spinel nickel lithium manganate cathode material and preparation method thereof |
| CN107681134A (en) * | 2017-09-07 | 2018-02-09 | 浙江瓦力新能源科技有限公司 | The preparation method of High-performance lithium manganate anode material |
| CN108539250A (en) * | 2018-03-30 | 2018-09-14 | 武汉艾特米克超能新材料科技有限公司 | A kind of solid lithium battery and preparation method thereof |
| WO2020083068A1 (en) * | 2018-10-23 | 2020-04-30 | 宁德时代新能源科技股份有限公司 | Positive electrode sheet, manufacturing method therefor, lithium ion secondary battery, battery module, battery pack, and device |
| CN111092194A (en) * | 2018-10-23 | 2020-05-01 | 宁德时代新能源科技股份有限公司 | Positive pole piece, preparation method thereof and lithium ion secondary battery |
| US11984589B2 (en) | 2018-10-23 | 2024-05-14 | Contemporary Amperex Technology Co., Limited | Positive-electrode plate and manufacturing method thereof, lithium-ion secondary battery, battery module, battery pack, and apparatus |
| CN109360988A (en) * | 2018-10-31 | 2019-02-19 | 云南民族大学 | A kind of nickel co-doped manganate cathode material for lithium preparation method of long-life high magnification aluminium |
| CN113120962A (en) * | 2021-03-20 | 2021-07-16 | 安徽博石高科新材料股份有限公司 | Gas-pressurized hydrothermal lithium manganate |
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