CN101841022A - Preparation method of lithium ion battery anode material lithium manganate - Google Patents
Preparation method of lithium ion battery anode material lithium manganate Download PDFInfo
- Publication number
- CN101841022A CN101841022A CN201010175808A CN201010175808A CN101841022A CN 101841022 A CN101841022 A CN 101841022A CN 201010175808 A CN201010175808 A CN 201010175808A CN 201010175808 A CN201010175808 A CN 201010175808A CN 101841022 A CN101841022 A CN 101841022A
- Authority
- CN
- China
- Prior art keywords
- lithium manganate
- powder
- anode material
- lithium
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000010405 anode material Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 title abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002244 precipitate Substances 0.000 claims abstract description 3
- 229910015645 LiMn Inorganic materials 0.000 claims description 11
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 206010013786 Dry skin Diseases 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 5
- 239000010416 ion conductor Substances 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 229910008686 LiaMn2-bMbO4 Inorganic materials 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 238000000605 extraction Methods 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 abstract 1
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 238000003780 insertion Methods 0.000 abstract 1
- 230000037431 insertion Effects 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000011572 manganese Substances 0.000 description 7
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 229910014077 LiMn1.9Cr0.1O4 Inorganic materials 0.000 description 3
- 229910014075 LiMn1.9Ni0.1O4 Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011533 mixed conductor Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229920002994 synthetic fiber Polymers 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a preparation method of a lithium ion battery anode material lithium manganate. Mixing Li (CH)3COO)·2H2O and Al (NO)3)3·9H2Adding O into ethylene glycol monomethyl ether, adding PO (OC) after completely dissolving4H9)3And Ti (OC)4H9)4And continuously stirring to ensure that the solution does not precipitate. Then adding LiaMn2-bMbO4Adding the powder into the prepared solution, and adding H while stirring3BO3Stirring, evaporating to dryness, drying, and drying to obtainCalcining the obtained powder in a muffle furnace, naturally cooling, and grinding to obtain the surface-coated yLi1+xAlxTi2-x(PO4)3·(1-y)Li3BO3Lithium manganate or doped lithium manganate powder. The lithium ion battery anode material prepared by the method has good cycle performance because the coating substance is a lithium ion conductor and cannot influence the insertion and extraction of lithium ions in the charging and discharging processes while effectively inhibiting the dissolution of lithium manganate.
Description
Technical field
The present invention relates to a kind of preparation method of lithium cell anode material lithium manganate.
Background technology
The positive electrode of commercialization lithium ion battery mostly is LiCoO at present
2Because Co scarcity of resources, its cost is far above negative pole, account for more than 1/3rd of battery total cost, make the large-scale application of lithium ion battery, especially the application in electric automobiles is restricted, thereby the cost that how to reduce anode material for lithium-ion batteries becomes the key of lithium ion battery material research.
At LiCoO
2, LiNiO
2And LiMn
2O
4In three kinds of common lithium ion battery 4V level positive electrodes, spinel lithium manganate is with low cost and environmentally friendly and become the research focus of anode material for lithium-ion batteries with it.LiMn
2O
4Shortcoming be that cycle performance is undesirable, influence LiMn
2O
4One of reason of cycle performance is LiMn in cyclic process
2O
4In Mn
3+Disproportionated reaction has taken place, the Mn of generation
2+Can be dissolved in the electrolyte, thereby cause the loss of active material and the destruction of crystal structure, cause the reduction of capacity.The present invention is at LiMn
2O
4And Li doped Mn
2O
4A kind of new coating processing is carried out on the surface, thereby suppresses the dissolving of LiMn2O4, improves LiMn
2O
4And Li doped Mn
2O
4Cycle performance.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of lithium cell anode material lithium manganate.
With Li (CH
3COO) 2H
2O and Al (NO
3)
39H
2O joins in the EGME, treats to dissolve fully the back and adds PO (OC
4H
9)
3And Ti (OC
4H
9)
4And constantly stir, guarantee that solution does not precipitate.Adopt solid phase or liquid phase reactor then, press the synthetic LiMn2O4 of known technology or doping type lithium manganate, i.e. Li
aMn
2-bM
bO
4(M=Cr, Ni; 0.96≤a≤1.06,0≤b≤0.1) powder.Then with Li
aMn
2-bM
bO
4Powder joins in the above-mentioned solution for preparing, and adds H when stirring
3BO
3, stir after 2 hours evaporate to dryness and 120 ℃ of dryings 2 hours, the powder that drying is obtained 750 ℃ of calcinings 0.5-5 hour in Muffle furnace, natural cooling, porphyrize obtain the surface and coat yLi
1+xAl
xTi
2-x(PO
4)
3(1-y) Li
3BO
3LiMn2O4 or doping type lithium manganate powder (wherein 0≤x≤2,0≤y≤1).
In whole process of preparation, Li (CH
3COO) 2H
2O, Al (NO
3)
39H
2O, Ti (OC
4H
9)
4, PO (OC
4H
9)
3, H
3BO
3The ratio of amount of substance be (1-3): (0-2): (0-2): (0-3): (0-1), and LiMn
2O
4And Li doped Mn
2O
4Surface coated mass percent is controlled in 10%.
Li
1+xAl
xTi
2-x(PO
4)
3Be a kind of lithium ion conductor of function admirable, its ionic conductivity reaches 7 * 10
-4S.cm
-1, and Li
3BO
3Be lithium ion conductor also be good flux, these two kinds of materials mix to coat can make the LiMn2O4 surface coat better, when effectively suppressing the LiMn2O4 dissolving, because coating material is lithium ion conductor, can not influence the embedding of lithium ion in the charge and discharge process and deviate from, thereby have better cycle performance.
Embodiment:
Embodiment 1
With Li
2CO
3(99%) and electrolytic manganese dioxide (99%) mix by the ratio of 1.05: 2 amount of substance, fully grinds and be placed in the Muffle furnace 530 ℃ of heat treatments 10 hours, and then in 750 ℃ of heat treatments 24 hours, product cooled off with stove, obtains LiMn
2O
4
With 0.7 mole of Li (CH
3COO) 2H
2O joins in 1200 milliliters of EGMEs, treats to dissolve fully the PO (OC that the back adds 0.075 mole
4H
9)
3Ti (OC with 0.05 mole
4H
9)
4And constantly stir, take by weighing 925 gram LiMn then
2O
4Join in the above-mentioned solution, add 0.225 mole H simultaneously again
3BO
3, said mixture is stirred after 2 hours in 80 ℃ of evaporates to dryness, 120 ℃ of dryings are 2 hours then, the powder that drying is obtained 750 ℃ of calcinings 1 hour in Muffle furnace, natural cooling, porphyrize obtain surperficial coated lithium ion mixed conductor 0.1LiTi
2(PO
4)
30.9Li
3BO
3LiMn
2O
4Powder, surface coated mass percent are 3%, and the initial capacity of synthetic material is 114mAh/g, and 300 circulation volume conservation rates are greater than 80%.
Embodiment 2
With Li
2CO
3(99%), electrolytic manganese dioxide (99%), Cr
2O
3Ratio by 1.05: 1.9: 0.1 amount of substances mixes, and fully grinds to be placed in the Muffle furnace 530 ℃ and to handle 10 hours, and then handles 24 hours in 750 ℃, and product cools off with stove, obtains LiMn
1.9Cr
0.1O
4
With 0.5375 mole of Li (CH
3COO) 2H
2O and 0.0375 mole of Al (NO
3)
39H
2O joins in 1600 milliliters of EGMEs, treats to dissolve fully the PO (OC that the back adds 0.375 mole
4H
9)
3Ti (OC with 0.2125 mole
4H
9)
4And constantly stir, take by weighing 1948 gram LiMn
1.9Cr
0.1O
4Join in the above-mentioned solution, and then add 0.125 mole H
3BO
3, constantly stir said mixture after 2 hours in 80 ℃ of evaporates to dryness, 120 ℃ of dryings are 2 hours then, the powder that drying is obtained 650 ℃ of calcinings 6 hours in Muffle furnace, natural cooling, porphyrize obtain surperficial coated lithium ion mixed conductor 0.5Li
1.3Al
0.3Ti
1.7(PO
4)
30.5Li
3BO
3LiMn
1.9Cr
0.1O
4Powder, surface coated mass percent are 3%, and the initial capacity of synthetic material is 117mAh/g, and 300 circulation volume conservation rates are greater than 80%.
Embodiment 3
With Li
2CO
3(99%), electrolytic manganese dioxide (99%), NiO be by 1.05: 1.9: 0.1 mixed in molar ratio, fully grinds to be placed in the Muffle furnace 530 ℃ and to handle 10 hours, and then handled 24 hours in 750 ℃, product cools off with stove, obtains LiMn
1.9Ni
0.1O
4
With 0.705 mole of Li (CH
3COO) 2H
2O and 0.405 mole of Al (NO
3)
39H
2O joins in 2000 milliliters of ethanol, treats to dissolve fully the PO (OC that the back adds 0.675 mole
4H
9)
3Ti (OC with 0.045 mole
4H
9)
4And constantly stir, take by weighing 2974 gram LiMn
1.9Ni
0.1O
4Join in the above-mentioned solution, and then add 0.075 mole H
3BO
3, constantly stir said mixture after 2 hours in 80 ℃ of evaporates to dryness, 120 ℃ of dryings are 2 hours then, the powder that drying is obtained 650 ℃ of calcinings 6 hours in Muffle furnace, natural cooling, porphyrize obtain surperficial coated lithium ion mixed conductor 0.9Li
2.8Al
1.8Ti
0.2(PO
4)
30.1Li
3BO
3LiMn
1.9Ni
0.1O
4Powder, surface coated mass percent are 3%, and the initial capacity of synthetic material is 115mAh/g, and 300 circulation volume conservation rates are greater than 80%.
Claims (3)
1. the preparation method of a lithium cell anode material lithium manganate is characterized in that the (CH with Li
3COO) 2H
2O and Al (NO
3)
39H
2O joins in the EGME, treats to dissolve fully the back and adds PO (OC
4H
9)
3And Ti (OC
4H
9)
4And constantly stir, guarantee that solution does not precipitate.Adopt solid phase or liquid phase reactor then, press the synthetic LiMn2O4 of known technology or doping type lithium manganate, i.e. Li
aMn
2-bM
bO
4(M=Cr, Ni; 0.96≤a≤1.06,0≤b≤0.1) powder.Then with Li
aMn
2-bM
bO
4Powder joins in the above-mentioned solution for preparing, and adds H when stirring
3BO
3, stir after 2 hours evaporate to dryness and 120 ℃ of dryings 2 hours, the powder that drying is obtained 750 ℃ of calcinings 0.5-5 hour in Muffle furnace, natural cooling, porphyrize obtain the surface and coat yLi
1+xAl
xTi
2-x(PO
4)
3(1-y) Li
3BO
3LiMn2O4 or doping type lithium manganate powder (wherein 0≤x≤2,0≤y≤1).
2. the preparation method of a kind of lithium cell anode material lithium manganate according to claim 1 is characterized in that Li (CH
3COO) 2H
2O, Al (NO
3)
39H
2O, Ti (OC
4H
9)
4, PO (OC
4H
9)
3, H
3BO
3The ratio of amount of substance be (1-3): (0-2): (0-2): (0-3): (0-1).
3. the preparation method of a kind of lithium cell anode material lithium manganate according to claim 1 is characterized in that LiMn
2O
4And Li doped Mn
2O
4Surface coated mass percent is controlled in 10%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010175808A CN101841022A (en) | 2010-05-13 | 2010-05-13 | Preparation method of lithium ion battery anode material lithium manganate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010175808A CN101841022A (en) | 2010-05-13 | 2010-05-13 | Preparation method of lithium ion battery anode material lithium manganate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101841022A true CN101841022A (en) | 2010-09-22 |
Family
ID=42744256
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010175808A Pending CN101841022A (en) | 2010-05-13 | 2010-05-13 | Preparation method of lithium ion battery anode material lithium manganate |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102332584A (en) * | 2011-10-18 | 2012-01-25 | 无锡晶石新型能源有限公司 | Liquid phase coating method of lithium manganate |
| CN103490055A (en) * | 2013-09-06 | 2014-01-01 | 中国海洋石油总公司 | Preparation method of nickel cobalt lithium manganate composite anode material |
| CN104183849A (en) * | 2014-08-12 | 2014-12-03 | 江苏大学 | Preparation method of solid solution positive material covering surface of fast ionic conductor |
| CN103456942B (en) * | 2013-08-20 | 2016-01-20 | 中信大锰矿业有限责任公司大新锰矿分公司 | A kind of LiMn2O4 liquid-coating method |
| CN107437619A (en) * | 2017-07-18 | 2017-12-05 | 南京创源天地动力科技有限公司 | A kind of anode for lithium battery material and preparation method thereof |
| CN109004212A (en) * | 2018-06-22 | 2018-12-14 | 中南大学 | A kind of big multiplying power manganate cathode material for lithium and preparation method thereof |
| CN111943272A (en) * | 2020-07-13 | 2020-11-17 | 广东邦普循环科技有限公司 | Method for eliminating residual lithium by lithium transition metal oxide and application thereof |
| US10930980B2 (en) | 2015-12-23 | 2021-02-23 | Industrial Technology Research Institute | Additive formulation and composition for lithium ion battery and lithium ion battery comprising the same |
| CN112635748A (en) * | 2019-10-09 | 2021-04-09 | 北京卫蓝新能源科技有限公司 | Composite positive electrode material of lithium ion battery and preparation method thereof |
Citations (1)
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| CN101038965A (en) * | 2006-03-14 | 2007-09-19 | 深圳市比克电池有限公司 | Method for preparing modified spinelle manganic acid lithium material and lithium secondary battery |
-
2010
- 2010-05-13 CN CN201010175808A patent/CN101841022A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101038965A (en) * | 2006-03-14 | 2007-09-19 | 深圳市比克电池有限公司 | Method for preparing modified spinelle manganic acid lithium material and lithium secondary battery |
Non-Patent Citations (1)
| Title |
|---|
| WU XIANMING ET AL: "Synthesis and characterization of Lil.3A10.3Til.7(P04)3一coated LiMn204 by wet chemical route", 《RARE METALS》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102332584A (en) * | 2011-10-18 | 2012-01-25 | 无锡晶石新型能源有限公司 | Liquid phase coating method of lithium manganate |
| CN102332584B (en) * | 2011-10-18 | 2013-09-18 | 无锡晶石新型能源有限公司 | Liquid phase coating method of lithium manganate |
| CN103456942B (en) * | 2013-08-20 | 2016-01-20 | 中信大锰矿业有限责任公司大新锰矿分公司 | A kind of LiMn2O4 liquid-coating method |
| CN103490055A (en) * | 2013-09-06 | 2014-01-01 | 中国海洋石油总公司 | Preparation method of nickel cobalt lithium manganate composite anode material |
| CN104183849A (en) * | 2014-08-12 | 2014-12-03 | 江苏大学 | Preparation method of solid solution positive material covering surface of fast ionic conductor |
| US10930980B2 (en) | 2015-12-23 | 2021-02-23 | Industrial Technology Research Institute | Additive formulation and composition for lithium ion battery and lithium ion battery comprising the same |
| CN107437619A (en) * | 2017-07-18 | 2017-12-05 | 南京创源天地动力科技有限公司 | A kind of anode for lithium battery material and preparation method thereof |
| CN109004212A (en) * | 2018-06-22 | 2018-12-14 | 中南大学 | A kind of big multiplying power manganate cathode material for lithium and preparation method thereof |
| CN112635748A (en) * | 2019-10-09 | 2021-04-09 | 北京卫蓝新能源科技有限公司 | Composite positive electrode material of lithium ion battery and preparation method thereof |
| CN112635748B (en) * | 2019-10-09 | 2022-11-15 | 北京卫蓝新能源科技有限公司 | Composite positive electrode material of lithium ion battery and preparation method thereof |
| CN111943272A (en) * | 2020-07-13 | 2020-11-17 | 广东邦普循环科技有限公司 | Method for eliminating residual lithium by lithium transition metal oxide and application thereof |
| CN111943272B (en) * | 2020-07-13 | 2022-11-15 | 广东邦普循环科技有限公司 | Method for eliminating residual lithium by lithium transition metal oxide and application thereof |
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Application publication date: 20100922 |