CN101841027A - Method for preparing lithium position rare earth-doped lithium vanadyl phosphate cathode material for lithium ion battery - Google Patents
Method for preparing lithium position rare earth-doped lithium vanadyl phosphate cathode material for lithium ion battery Download PDFInfo
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- CN101841027A CN101841027A CN201010175794A CN201010175794A CN101841027A CN 101841027 A CN101841027 A CN 101841027A CN 201010175794 A CN201010175794 A CN 201010175794A CN 201010175794 A CN201010175794 A CN 201010175794A CN 101841027 A CN101841027 A CN 101841027A
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- lithium
- rare earth
- ball
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- vanadyl phosphate
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Abstract
The invention discloses a method for preparing a lithium position rare earth-doped lithium vanadyl phosphate cathode material for a lithium ion battery. The cathode material has a nominal formation formula: Li(1-3x)RExVOPO4, which is prepared by the method comprising the steps as follows: mixing a lithium source, a rare earth source, a vanadium source and a phosphorus source according to a certain ratio, adding dispersant for mixed ball milling to obtain colloid in a rheological state, drying the colloid and grinding into fine powder, and sintering at a certain atmosphere to obtain the lithium position rare earth-doped lithium vanadyl phosphate powder with the formation formula of Li(1-3x)RExVOPO4. The invention can prepare the lithium position rare earth-dope lithium vanadyl phosphate cathode materal powder for a secondary lithium ion battery with favorable crystallinity and uniform components by adopting a rheological phase method and a simple mixed ball-milling drying technology, and controlling the heat treatment temperature and time, and the primary discharge specific capacity is more than 140mAh/g at room temperature. Compared with pure lithium vanadyl phosphate, the invention can obviously improve parent capacity and circulation performance, especially the multiplying power circulation performance, and the material synthesis process is suitable for industrialized production.
Description
Technical field
The present invention relates to the preparation method of the lithium position rare earth-doped vanadyl phosphate lithium anode material of a kind of lithium ion battery.
Background technology
The develop rapidly of IT industry, mobile communication, electronic equipment and electric automobile has proposed new requirement to anode material for lithium ion battery.In numerous positive electrodes, lithium cobalt oxygen (LiCoO
2) function admirable, but cobalt resource is rare, lithium cobalt oxygen number Ge Gaoang, and security performance is not good enough, has limited its application in the electric automobile field.Though other layered oxide also can obtain specific capacity up to 150mAh/g (as LiNi
1/3Co
1/3Mn
1/3O
2), but the thermal stability under the deep charge state is low, security performances such as the stability of overcharging shortcoming.Spinel structure compound L iMn
2O
4Theoretical capacity is up to 148mAh/g, and Stability Analysis of Structures, security performance (stability of overcharging) are good, but (as 55 ℃) stripping Mn easily under the high temperature
3+, cause capacity attenuation.Transition metal phosphate has been subjected to paying close attention to widely, and has been expected to replace lithium cobalt oxygen as novel positive electrode owing to oxidation-reduction potential height, good and outstanding electrochemical properties and the thermal stability of ionic conductivity.Wherein, the most representative LiFePO
4(theoretical capacity is 169mAh/g), raw material sources are abundant, environmental friendliness, discharging voltage balance, have high security, high-temperature stable and good cycle characteristics and become the research focus.But its discharge voltage is 3.3-3.5V with respect to lithium metal, and discharge voltage is relatively low, in addition, and LiFePO
4Energy density, electronic conductivity and tap density are also low, and multiplying power discharging property is poor, particularly LiFePO
4Very responsive to synthetic atmosphere (must be the atmosphere of reproducibility) and synthesis temperature, be unfavorable for low-cost large-scale production.These shortcomings have greatly limited LiFePO
4Further develop and commercialization.
And another li-contained phosphate-vanadyl phosphate lithium (LiVOPO
4) caused people's attention.LiVOPO
4Theoretical specific capacity be 159mAh/g, Stability Analysis of Structures, discharge voltage and other positive active material be (is 3.8-3.9V with respect to lithium metal) quite, and synthetic also relatively easy.In addition, the resource of vanadium is very abundant, and its price is also much lower than cobalt, considers from material cost, and research and development Li-V is that positive electrode compares LiCoO in China
2Positive electrode has more practical significance.
LiVOPO
4The maximum bottleneck that is applied to lithium ion battery as positive electrode is LiVOPO
4Electronic conductivity diffusion coefficient low and lithium ion less, press conventional art merely with LiVOPO
4Mix with conductive auxiliary agent, be difficult to head it off.
In fact, the method that improves material electronics conductivity is a lot, mainly comprises two kinds of bulk phase-doped and surperficial coatings.As: literature research shows, to LiFePO
4Lithium position doped metal ion (as Na
+, rare earth element etc.) can effectively improve electron conduction in the fertile material lattice.And adopt coated with carbon or metal to improve a kind of especially lithium ion battery electrode material modified method that is widely used of the intergranular electronic conductivity of fertile material.
Summary of the invention
The object of the present invention is to provide the preparation method of the lithium position rare earth-doped vanadyl phosphate lithium anode material of a kind of lithium ion battery, the nominal composition formula of material is Li
1-3xRE
xVOPO
4, wherein, 0＜x＜0.05.Be about to lithium source (lithium carbonate, lithium oxalate, lithium acetate, a kind of in the lithium hydroxide), rare earth source (the lanthanum in the lanthanide series except that promethium, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, the oxide of lutetium trivalent rare earth element, chloride, nitrate, sulfate, carbonate, a kind of in fluoride or the organic salt), vanadium source (vanadic oxide, ammonium metavanadate a kind ofly) and phosphorus source (diammonium hydrogen phosphate, a kind of in ammonium dihydrogen phosphate or the ammonium phosphate) ratio by amount of substance is Li: RE: V: P=(1-3x): x: 1: 1 raw materials weighing, wherein, 0＜x＜0.05, add zirconia ball then, the corundum ball, agate ball, stainless steel ball, a kind of in the polyurethane ball as ball-milling medium and deionized water, industrial alcohol, absolute ethyl alcohol, the mixture of one or more in the acetone as dispersant at the corundum ball grinder, agate jar, the polyurethane ball grinder, mixing and ball milling 4-6h in nylon ball grinder or the tungsten carbide ball milling jar, obtain rheology attitude jelly, jelly is ground to form fine powder behind 60-80 ℃ of dry 2h, again in air-flow velocity be the 0.1-8.0 liter/minute nitrogen or argon gas atmosphere in 400 ℃ of-800 ℃ of sintering 6-10h, obtain the lithium position rare earth-doped vanadyl phosphate lithium powder of nominal composition formula.
Can prepare with method of the present invention that crystallinity is good, the uniform lithium position rare earth-doped vanadyl phosphate lithium anode material of composition, first discharge specific capacity is greater than 140mAh/g under the room temperature.Compare with pure phosphoric acid vanadyl lithium, the present invention has significantly improved particularly high rate capability of parent capacity and cycle performance, is applicable to suitability for industrialized production simultaneously.
Embodiment:
Embodiment 1
By Li: La: V: P=0.994: the ratio of 0.002: 1: 1 amount of substance takes by weighing analyzes pure level lithium carbonate (Li
2CO
3) 7.345g, analyze pure level lanthanum oxalate (La
2(C
2O
4)
39H
2O) 0.0565g analyzes pure level ammonium metavanadate (NH
4VO
3) 11.698g, analyze pure level ammonium di-hydrogen phosphate (NH
4H
2PO
4) 11.503g, mixing the back adds in the nylon ball grinder, add the 60mL absolute ethyl alcohol again, sealing back is ball-milling medium ball milling 4h with the zirconia ball on planetary ball mill, obtain rheology attitude jelly, jelly is ground to form fine powder behind 80 ℃ of dry 2h, again in flow velocity be in 0.5 liter of/minute argon gas atmosphere in 600 ℃ of sintering 8h, obtaining nominal composition formula is Li
0.994La
0.002VOPO
4The positive electrode powder.
The chemical property of gained sample is measured as follows: with mass fraction is that 80% sample, 10% acetylene black and 10% Kynoar (PVDE) mix, and be dissolved in and form slurry in the solvent N-methyl pyrrolidone (NMP), slurry is evenly coated on the aluminium foil, and the thickness of coating is about 100um.It is 1cm that the electrode slice that coats is cut into area
2Work electrode.Standby at 60 ℃ of following vacuumize 12h.Test battery adopts conventional button cell, is to electrode with metallic lithium foil, 1.0molL
-1LiPF
6Ethyl carbonate (EC)/dimethyl carbonate (DMC) (volume ratio is 1: 1) solution be electrolyte, in being full of the glove box of argon gas, be assembled, digestion time is 6h.Speed by 16mA/g (in positive pole) charges to 4.3V, is discharged to 3.0V, and discharge curve obtains the stable discharge voltage plateau of 3.85V first, and reversible specific capacity is about 149mAh/g first, and specific discharge capacity is greater than 140mAh/g after 30 circulations.
Embodiment 2
By Li: La: V: P=0.988: 0.004: 1: 1 amount of substance ratio takes by weighing analyzes pure level lithium carbonate (Li
2CO
3) 7.300g, analyze pure level lanthanum oxalate (La
2(C
2O
4)
39H
2O) 0.113g analyzes pure level ammonium metavanadate (NH
4VO
3) 11.698g, analyze pure level ammonium di-hydrogen phosphate (NH
4H
2PO
4) 11.503g, mixing the back adds in the corundum ball grinder, add 60mL acetone again, sealing back is ball-milling medium ball milling 6h with the agate ball on planetary ball mill, obtain rheology attitude jelly, jelly is ground to form fine powder behind 80 ℃ of dry 2h, again in flow velocity be in 1.0 liters/minute the argon gas atmosphere in 600 ℃ of sintering 8h, obtaining nominal composition formula is Li
0.988La
0.004VOPO
4The positive electrode powder.
The chemical property of gained sample is measured as follows: with mass fraction is 80% sample, 10% acetylene black and 10% Kynoar (PVDE), makes electrode slice and is assembled into battery by embodiment 1.Speed by 16mA/g (in positive pole) charges to 4.3V, is discharged to 3.0V, and discharge curve obtains the stable discharge voltage plateau of 3.85V first, and reversible specific capacity is about 151mAh/g first, and specific discharge capacity is greater than 140mAh/g after 30 circulations.
Embodiment 3
By Li: Ce: V: P=0.991: 0.003: 1: 1 amount of substance ratio takes by weighing analyzes pure level lithium carbonate (Li
2CO
3) 7.323g, analyze pure level cerium oxalate (Ce
2C
2O
4)
39H
2O) 0.106g analyzes pure level ammonium metavanadate (NH
4VO
3) 11.698g, analyze pure level ammonium di-hydrogen phosphate (NH
4H
2PO
4) 11.503g, mixing the back adds in the corundum ball grinder, add the 60mL deionized water again, sealing back is ball-milling medium ball milling 4h with the stainless steel ball on planetary ball mill, obtain rheology attitude jelly, jelly is ground to form fine powder behind 80 ℃ of dry 2h, again in flow velocity be in 1.0 liters/minute the argon gas atmosphere in 600 ℃ of sintering 10h, obtaining nominal composition formula is Li
0.991Ce
0.003VOPO
4The positive electrode powder.
The chemical property of gained sample is measured as follows: with mass fraction is 80% sample, 10% acetylene black and 10% Kynoar (PVDE), makes electrode slice and is assembled into battery by embodiment 1.Speed by 16mA/g (in positive pole) charges to 4.3V, is discharged to 3.0V, and discharge curve obtains the stable discharge voltage plateau of 3.83V first, and reversible specific capacity is about 147mAh/g first, and specific discharge capacity is greater than 140mAh/g after 30 circulations.
Claims (6)
1. the preparation method of the lithium position rare earth-doped vanadyl phosphate lithium anode material of lithium ion battery, the nominal composition formula that it is characterized in that material is Li
1-3xRE
xVOPO
4, wherein, 0＜x＜0.05; Lithium source, rare earth source, vanadium source and phosphorus source are pressed the ratio Li of amount of substance: RE: V: P=(1-3x): x: 1: 1 raw materials weighing; add ball-milling medium and dispersant mixing and ball milling 4-6h in ball grinder then; obtain rheology attitude jelly; jelly is ground to form fine powder behind 60-80 ℃ of dry 2h; again in protective atmosphere in 400 ℃ of-800 ℃ of sintering 6-10h, obtain the lithium position rare earth-doped vanadyl phosphate lithium powder of nominal composition formula.
2. the preparation method of the lithium position rare earth-doped vanadyl phosphate lithium anode material of lithium ion battery according to claim 1, it is characterized in that the lithium source is lithium carbonate or lithium oxalate or lithium acetate or lithium hydroxide, the rare earth source is a kind of in oxide, chloride, nitrate, sulfate, carbonate, fluoride or the organic salt of the lanthanum except that promethium in the lanthanide series, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium trivalent rare earth element, the vanadium source is vanadic oxide or ammonium metavanadate, and the phosphorus source is diammonium hydrogen phosphate or ammonium dihydrogen phosphate or ammonium phosphate.
3. the preparation method of the lithium position rare earth-doped vanadyl phosphate lithium anode material of lithium ion battery according to claim 1, it is characterized in that ball-milling medium is zirconia ball or corundum ball or agate ball or stainless steel ball or polyurethane ball, dispersant is deionized water or industrial alcohol or absolute ethyl alcohol or acetone.
4. according to the preparation method of claim 1 or the lithium position rare earth-doped vanadyl phosphate lithium anode material of 3 described lithium ion batteries, it is characterized in that ball grinder is corundum ball grinder or agate jar or polyurethane ball grinder or nylon ball grinder or tungsten carbide ball milling jar.
5. the preparation method of the lithium position rare earth-doped vanadyl phosphate lithium anode material of lithium ion battery according to claim 1 is characterized in that protective atmosphere is nitrogen or argon gas.
6. the preparation method of the lithium position rare earth-doped vanadyl phosphate lithium anode material of lithium ion battery according to claim 1 or 5, it is characterized in that the protective atmosphere air-flow velocity be the 0.1-8.0 liter/minute.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102709552A (en) * | 2012-05-22 | 2012-10-03 | 吉首大学 | Preparation method of iron-doped lithium vanadium oxygen phosphate (LiVOPO4) positive material for lithium ion battery |
| CN103259005A (en) * | 2013-05-08 | 2013-08-21 | 深圳市斯诺实业发展有限公司永丰县分公司 | Method for preparing high-capacity high-magnification lithium ion battery cathode material |
| CN104752722A (en) * | 2015-03-18 | 2015-07-01 | 北京理工大学 | Doped modified lithium vanadium phosphate anode material as well as preparation method and application thereof |
| CN109817968A (en) * | 2017-11-21 | 2019-05-28 | 宁德时代新能源科技股份有限公司 | Surface-coated lithium nickel manganese oxide particles and method for producing same |
| CN112125340A (en) * | 2020-09-18 | 2020-12-25 | 厦门厦钨新能源材料股份有限公司 | Lithium manganate and preparation method and application thereof |
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| CN101567449A (en) * | 2009-06-02 | 2009-10-28 | 徐瑞松 | Nano-level lithium cell anodic material and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102709552A (en) * | 2012-05-22 | 2012-10-03 | 吉首大学 | Preparation method of iron-doped lithium vanadium oxygen phosphate (LiVOPO4) positive material for lithium ion battery |
| CN103259005A (en) * | 2013-05-08 | 2013-08-21 | 深圳市斯诺实业发展有限公司永丰县分公司 | Method for preparing high-capacity high-magnification lithium ion battery cathode material |
| CN103259005B (en) * | 2013-05-08 | 2015-08-19 | 深圳市斯诺实业发展有限公司 | A kind of preparation method of high power capacity high rate lithium ionic cell cathode material |
| CN104752722A (en) * | 2015-03-18 | 2015-07-01 | 北京理工大学 | Doped modified lithium vanadium phosphate anode material as well as preparation method and application thereof |
| CN109817968A (en) * | 2017-11-21 | 2019-05-28 | 宁德时代新能源科技股份有限公司 | Surface-coated lithium nickel manganese oxide particles and method for producing same |
| CN112125340A (en) * | 2020-09-18 | 2020-12-25 | 厦门厦钨新能源材料股份有限公司 | Lithium manganate and preparation method and application thereof |
| CN112125340B (en) * | 2020-09-18 | 2022-05-17 | 厦门厦钨新能源材料股份有限公司 | Lithium manganate and preparation method and application thereof |
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Application publication date: 20100922 |