CN102299325B - Ionothermal process of manganese lithium phosphate anode material - Google Patents
Ionothermal process of manganese lithium phosphate anode material Download PDFInfo
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- CN102299325B CN102299325B CN201110215281.9A CN201110215281A CN102299325B CN 102299325 B CN102299325 B CN 102299325B CN 201110215281 A CN201110215281 A CN 201110215281A CN 102299325 B CN102299325 B CN 102299325B
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- manganese
- lithium
- anode material
- phosphate
- lithium phosphate
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Abstract
The invention relates to an ionothermal process of a manganese lithium phosphate anode material. The process is characterized in that a lithium source, a manganese source and a phosphate source are proportioned according to a mole ratio of 3:1:1 and then added into alcamines ionic liquid, a proper amount of additive is added and reacted for 1-12 hours under the 110 DEG C-230 DEG C for 1-12 hours to obtain the manganese lithium phosphate; a carbon source is mixed and carried out a calcining treatment at high temperature to obtain a LiMnPO anode material with the high specific capacity of 153mAh/g. According to the invention, the ionothermal process of a manganese lithium phosphate anode material under the normal pressure and low temperature is capable of avoiding the requirement of high-pressure by a hydrothermal method; the ionic liquid can be a reaction medium as well as a structure regulator of crystal growth, the ionothermal process of the invention is a novel preparation method of the manganese lithium phosphate anode material.
Description
One, technical field
The invention belongs to method for preparing anode material of lithium-ion battery, specifically a kind of preparation method of lithium-manganese phosphate anode material for lithium ion battery.
Two, background technology
LiMnPO
4theoretical capacity and LiFePO
4identical, be 170mAh g
-1but it is relative to Li
+electrode potential be 4.1v, far above LiFePO
43.4V voltage platform, and be positioned at the stable electrochemical window of existing electrolyte system.The high potential of 4.1V makes LiMnPO
4have the advantage of potential high-energy-density, this is that it is relative to LiFePO
4sharpest edges, if LiMnPO
4actual capacity perform to and LiFePO
4identical degree, its energy density will compare LiFePO
4high by 35%.Therefore, this material shows very strong attraction.
LiMnPO
4preparation method with and LiFePO
4substantially identical Deng material, mainly contain high temperature solid phase synthesis, hydro thermal method, coprecipitation and sol-gel process etc.At present, a kind of method of anode material for lithium-ion batteries of synthesis newly---ion thermal synthesis method occurs.
The concept of ion thermal synthesis is proposed in 2004 by the people such as Cooper E professor R of St.Andrews university of Britain at first, report the molecular sieve using ionic liquid (ionic liquid is [emim] Br, i.e. 1-ethyl-3-methyllimidazolium bromide) to synthesize a kind of new structure as solvent and template.After this, the research utilizing ion process for thermosynthesizing to prepare inorganic material is just carried out gradually.2009, ion thermal synthesis was introduced field prepared by anode material for lithium-ion batteries by the N.Recham of France etc., in a series of glyoxaline ion liquid, synthesized olivine-type LiMnPO
4positive electrode.Subsequently, a series of positive electrode, as LiMnPO
4f, LiTiPO
4f, Li (Mn
1-xm
x) SO
4f (M=Co, Ni, Mn), Na
2mPO
4f (M=Mn, Mn) etc. is synthesized out in ionic liquid.
Ion thermal synthesis method refers to and replaces conventional water or the organic solvent material synthesis method as reaction medium with ionic liquid (comprising low eutectic mixture).Utilize the hot legal system of ion for compared with the hydro-thermal of anode material for lithium-ion batteries and routine and solvent process for thermosynthesizing, ion thermal synthesis reaction can be carried out at ambient pressure, this mainly ionic liquid chance there is no vapour pressure, therefore ion thermal method is prepared anode material for lithium-ion batteries and can not be used autoclave.Due to alternative ionic liquid kind and number various, therefore use dissimilar ionic liquid just likely to synthesize the material of many new structures.In addition, the another one feature of ion process for thermosynthesizing is exactly that used ionic liquid can be recycled, and this meets the requirement of society for environmental protection very much.
Three, summary of the invention
The present invention aims to provide a kind of method with the manganese-lithium phosphate anode material of good electrical chemical property utilizing novel ion thermal synthesis method to prepare.
Technical solution problem of the present invention adopts following technical scheme: be first add in alcamines ionic liquid at 1: 1 in molar ratio by manganese source and phosphorus source, after mixing, then is 1: 1 ~ 3 add lithium source by manganese source and lithium source mol ratio; At 110 DEG C ~ 230 DEG C, stirring reaction 1 ~ 12 hour under the condition of normal pressure, after being cooled to room temperature through being separated, washing and drying obtain lithium manganese phosphate (LiMnPO
4); Then after the carbon source adding lithium manganese phosphate mass fraction 3 ~ 8% mixes, 400 DEG C ~ 750 DEG C calcinings 1 ~ 10 hour under inert atmosphere protection, obtain the coated manganese-lithium phosphate anode material (LiMnPO of charcoal
4/ C).
Described manganese source is selected from one or more in manganese sulfate, manganese acetate, manganese lactate, manganese chloride, manganese oxalate.
Described phosphorus source is selected from one or more in phosphoric acid, lithium dihydrogen phosphate, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, sodium phosphate.
Described lithium source is selected from one or more in a hydronium(ion) lithia, lithium carbonate, lithium oxalate, lithium acetate, lithium chloride, lithium nitrate, lithium sulfate.
Described carbon source is selected from one or more in glucose, citric acid, sucrose, starch.
Described alcamines ionic liquid is selected from one or more in monoethanolamine acetate, ethanolamine lactate, diethanol amine acetate, diethanol amine lactate, dimethylethanolamine acetate, dimethylethanolamine lactate, triethanolamine acetate, triethanolamine lactate.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, process provides a kind of hot method technology of preparing of ion of manganese-lithium phosphate anode material of atmospheric low-temperature, hydro thermal method can be avoided the requirement of high pressure, poor repeatability and the high energy consumption of high temperature solid-state method technique can be overcome again; Ionic liquid had not only been made solvent but also had been the stay in place form of crystal growth, was easy to obtain even particle distribution, finely disseminated manganese-lithium phosphate anode material.
2, this method is used for the ionic liquid of solvent and structure growth template in the synthesis of ion hot method is alcamines ionic liquid, and such ionic liquid has and is easy to synthesis, and cost is lower, the feature of Heat stability is good, and realizes recycling by being separated.
3, this method synthesis condition is gentleer, and energy consumption is lower, is easy to realize suitability for industrialized production.
Four, accompanying drawing explanation
Fig. 1 is the XRD figure of the lithium manganese phosphate without high-temperature process according to embodiment 1 preparation
Fig. 2 is the XRD figure of the coated manganese-lithium phosphate anode material of charcoal according to embodiment 1 preparation
Fig. 3 is the SEM figure of the coated manganese-lithium phosphate anode material of charcoal according to embodiment 1 preparation
Fig. 4 is the cycle performance figure of the coated manganese-lithium phosphate anode material of charcoal according to embodiment 1 preparation
Five, embodiment
Embodiment 1:
By 24.51g (CH
3cOO)
2mn4H
2o and 11.49g H
3pO
4add in the round-bottomed flask that 250ml ionic liquid of ethanolamine lactate is housed, after mixing, add 12.59g LiOHH
2o.At 200 DEG C, stirring reaction 6 hours under normal pressure, after cooling, product washed, be separated, drying obtains lithium manganese phosphate.Be mixed into after the carbon source sucrose accounting for lithium manganese phosphate mass fraction 5% under argon gas atmosphere protection, 600 DEG C of high-temperature calcinations 3 hours, obtain the coated manganese-lithium phosphate anode material of charcoal.
X-ray diffractogram before and after high-temperature process is shown in Fig. 1 and Fig. 2 respectively, shows that product is the LiMnPO of well-crystallized
4; SEM figure Fig. 3 of the coated manganese-lithium phosphate anode material of charcoal after high-temperature process, can find out even particle distribution, good dispersion.
The coated manganese-lithium phosphate anode material of charcoal of preparation in embodiment 1, acetylene black and PVDF are made into slurry with mass ratio 8: 1: 1 mixing, on even application to aluminum foil current collector, drying obtains positive plate, using metal lithium sheet as negative pole, microporous polypropylene membrane is barrier film, 1mol/L LiPF
6(volume ratio of solvent is ethylene carbonate and the dimethyl carbonate mixed liquor of 1: 1), as electrolyte, is assembled into button simulated battery in the glove box of high-purity argon gas protection.
After tested, the first charge-discharge curve of gained manganese-lithium phosphate anode material is as Fig. 4, and under the multiplying power of 0.1C, the discharge capacity of material is 151.3mAh/g.
Embodiment 2:
By 16.9g MnSO
4h
2o and 11.49g H
3pO
4add in the round-bottomed flask that 250ml triethanolamine acetate ionic liquid is housed, after mixing, add 12.59g LiOHH
2o.200 DEG C, reaction 6 hours under normal pressure, after cooling, product washed, be separated, drying obtains lithium manganese phosphate.Be mixed into after the carbon source sucrose accounting for lithium manganese phosphate mass fraction 8% under argon gas atmosphere protection, 600 DEG C of high-temperature calcinations 3 hours, obtain the coated manganese-lithium phosphate anode material of charcoal.
Embodiment 3:
By 25.1g Mn (NO
3)
24H
2o and 11.49g H
3pO
4add in the round-bottomed flask that 250ml monoethanolamine acetate ion liquid is housed, after mixing, add 20.69g LiNO
3, at 110 DEG C, stirring reaction 12 hours under normal pressure, after cooling, product washed, be separated, drying obtains lithium manganese phosphate.Be mixed into after the carbon source glucose accounting for lithium manganese phosphate mass fraction 3% under argon gas atmosphere protection, 500 DEG C of high-temperature calcinations 8 hours, obtain the coated manganese-lithium phosphate anode material of charcoal.
Embodiment 4:
By 14.3g MnC
2o
42H
2o and 11.50g NH
4h
2pO
4add in the round-bottomed flask that 250ml diethanol amine lactate ions liquid is housed, after mixing, add 38.39g Li
2sO
4h
2o, at 230 DEG C, stirring reaction 1 hour under normal pressure, washs product after cooling, is separated, drying obtains lithium manganese phosphate.Be mixed into after the carbon source starch accounting for lithium manganese phosphate mass fraction 6% under argon gas atmosphere protection, 600 DEG C of high-temperature calcinations 3 hours, obtain the coated manganese-lithium phosphate anode material of charcoal.
Embodiment 5:
By 19.8g MnCl
24H
2o and 13.61g KH
2pO
4add in the round-bottomed flask that 250ml triethanolamine lactate ions liquid is housed, after mixing, add 12.72g LiCl, at 180 DEG C, stirring reaction 6 hours under normal pressure, after cooling, product washed, be separated, drying obtains lithium manganese phosphate.Be mixed into after the carbon source citric acid accounting for lithium manganese phosphate mass fraction 5% under argon gas atmosphere protection, 750 DEG C of high-temperature calcinations 1 hour, obtain the coated manganese-lithium phosphate anode material of charcoal.
Embodiment 6:
By 16.9g MnSO
4h
2o and 12.0g NaH
2pO4 adds in the round-bottomed flask that 250ml ionic liquid of ethanolamine lactate is housed, and adds 22.17g Li after mixing
2cO
3, at 200 DEG C, stirring reaction 6 hours under normal pressure, after cooling, product washed, be separated, drying obtains lithium manganese phosphate.Be mixed into after the carbon source sucrose accounting for lithium manganese phosphate mass fraction 5% under argon gas atmosphere protection, 400 DEG C of high-temperature calcinations 10 hours, obtain the coated manganese-lithium phosphate anode material of charcoal.
Claims (1)
1. a preparation method for lithium-manganese phosphate anode material for lithium ion battery, is characterized in that: by 24.51g (CH
3cOO)
2mn4H
2o and 11.49gH
3pO
4add in the round-bottomed flask that 250ml ionic liquid of ethanolamine lactate is housed, after mixing, add 12.59gLiOHH
2o; At 200 DEG C, stirring reaction 6 hours under normal pressure, after cooling, product washed, be separated, drying obtains lithium manganese phosphate; Be mixed into after the carbon source sucrose accounting for manganese phosphate mass fraction 5% under argon gas atmosphere protection, 600 DEG C of high-temperature calcinations 3 hours, obtain the coated manganese-lithium phosphate anode material of charcoal; Coated for described charcoal manganese-lithium phosphate anode material, acetylene black and PVDF are made into slurry with mass ratio 8: 1: 1 mixing, and on even application to aluminum foil current collector, drying obtains positive plate, and using metal lithium sheet as negative pole, microporous polypropylene membrane is barrier film, 1mol/L LiPF
6as electrolyte, the solvent of described electrolyte to be volume ratio be 1: 1 ethylene carbonate and dimethyl carbonate mixed liquor, in the glove box of high-purity argon gas protection, be assembled into battery; After tested, under the multiplying power of 0.1C, the discharge capacity of material is 151.3mAh/g.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103258994B (en) * | 2013-05-06 | 2015-06-24 | 天津巴莫科技股份有限公司 | Positive material for lithium ion battery, preparation method of material, and lithium ion battery |
| CN103337628B (en) * | 2013-06-18 | 2015-11-18 | 常州大学 | A kind of synthetic method of positive material nano lithium manganese phosphate of lithium ion battery |
| CN103570074B (en) * | 2013-11-11 | 2015-10-21 | 甘肃大象能源科技有限公司 | A kind of manganate cathode material for lithium and preparation method thereof |
| CN104091951A (en) * | 2014-07-23 | 2014-10-08 | 中国科学技术大学苏州研究院 | Method for synthesizing LiMnPO4/C by mixed carbon source |
| CN104779374A (en) * | 2015-04-23 | 2015-07-15 | 天津巴莫科技股份有限公司 | Preparation method of high-performance hollow manganese lithium phosphate for lithium ion powder battery |
| CN105720253A (en) * | 2016-02-26 | 2016-06-29 | 广西大学 | Carbon-coated lithium manganese phosphate cathode material and preparation method thereof |
| CN106957049B (en) * | 2017-05-09 | 2019-01-29 | 东北大学 | A method of preparing nanoscale lithium manganese phosphate |
| CN112018364B (en) * | 2020-09-05 | 2022-10-04 | 河南科技学院 | Equimolar hydrothermal method for preparing LiMnPO 4 Method for preparing composite material and application of composite material in lithium battery |
| CN112456464A (en) * | 2020-11-25 | 2021-03-09 | 安徽工业大学 | Method for preparing electrode material by using eutectic salt |
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| CN101269821A (en) * | 2008-05-07 | 2008-09-24 | 中国科学院过程工程研究所 | Ion thermal method for preparing molecular sieve in alcohol amine ion liquid |
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| CN101269821A (en) * | 2008-05-07 | 2008-09-24 | 中国科学院过程工程研究所 | Ion thermal method for preparing molecular sieve in alcohol amine ion liquid |
Non-Patent Citations (1)
| Title |
|---|
| Ionthermal Synthesis and Electrochemical Characterization of Nanostructured Lithium Manganese Phosphates;Prabeer Barpanda etal;《ECS Transactions》;20101231;第25卷(第14期);摘要，第2页第1-2段 Experimental，第3页第1-2段Results and Discussion * |
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