CN102280621A - Method for preparing lithium ion battery material lithium and manganese phosphate/carbon by adopting sol-gel method - Google Patents
Method for preparing lithium ion battery material lithium and manganese phosphate/carbon by adopting sol-gel method Download PDFInfo
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Abstract
The invention relates to a method for preparing a lithium ion battery material lithium and manganese phosphate/carbon by adopting a sol-gel method, belonging to the technical field of new energy materials. The preparation method comprises the following steps of: dissolving or dispersing a lithium source compound, a manganese source compound, a phosphorus source compound and a complexant compound according to a mol ratio of 1.025: 1: 1: (0-2) in a solvent to obtain a mixed material; adjusting the pH value of the solution to be 0.5-3.7 by adopting concentrated nitric acid or stronger ammonia water to obtain a sol solution; and drying the sol solution in a water bath kettle by distillation to obtain xerogel, then drying and roasting to obtain carbon-coated lithium and manganese phosphate with granularity of 50-150nm. The material which is provided with a lithium and manganese phosphate substrate and externally coated with a carbon material, synthesized by adopting the method, has nano-scale size and dispersion uniformity and has the capabilities of effectively preventing particles from agglomerating and improving the electron conductivity of the particles. An electrochemical test indicates that: an electrode has a remarkable discharge platform in about 4V and has high discharge capacity and good circular stability.
Description
Technical field
The present invention relates to a kind of method that adopts sol-gel to prepare lithium ion battery material lithium manganese phosphate/carbon, belong to energy new material technology field.
Background technology
Positive electrode is the important component part of lithium rechargeable battery, mainly contains LiCoO at present
2, LiNiO
2, LiMn
2O
4Deng.LiCoO
2Toxicity is big, costs an arm and a leg, and has certain safety problem; LiNiO
2Cost is low, and capacity is higher, but the preparation difficulty, and also there is comparatively serious safety problem in the poor reproducibility of thermal stability and material; Spinelle LiMn
2O
4Cost is low, and security performance is good, but capacity is low, and cycle performance especially high temperature cyclic performance is poor.Therefore, the positive electrode of development function admirable just becomes one of popular domain of present lithium ion battery material research.
In recent years, phosphate is because they have low toxicity, lower cost, better chemical stability and thermal stability as possible anode material for lithium-ion batteries.Oxonium ion in the olivine structural and P
5+And PO
4 3-The tetrahedron polyanionic forms strong covalent bond to stablize three-dimension-framework.In all kinds of transition metal phosphate positive electrodes, LiMnPO
4Provide with respect to Li
+The redox potential of the 4.1V of/Li is expected to become follow-on anode material for lithium-ion batteries.But lithium manganese phosphate locks into low intrinsic electronics and ionic conductivity, thereby discharge rate is slow, and chemical property is poor especially under high current density, mainly is because the cause of intragranular lithium diffusion slowly and low intrinsic electronic conductivity.Therefore, in order to improve its performance, the approach of taking has: the one, increase the intrinsic electronic conductivity by cation doping; Be minimization of particle size in addition, thereby shorten the diffusion path length of lithium ion in the cathode material, increase contact area with conductive additive such as carbon with the olivine material.
At present synthetic LiMnPO
4Method mainly contain high-temperature solid phase reaction method, liquid-phase coprecipitation, hydro thermal method etc.Wherein the use of high-temperature solid phase reaction method is the most extensive, and the emerging research group of domestic Wang Zhi has carried out research for many years to this, and its typical building-up process is formed LiMnPO for pressing
4Stoichiometric proportion get Li
2CO
3, MnCO
3, NH
4H
2PO
4, and mix with an amount of carbon black ball milling, and then calcining obtains product in the inert atmosphere, but there is the low problem of purity of sintetics in this method.Delacourt etc. have synthesized the LiMnPO of 100nm diameter by precipitation
4Particle, its 70mAh/g that only 35mAh/g during from 1 μ m diameter particle is increased at C/20 with reversible capacity.Yonemura etc. have reached discharge capacity at the 150mAh/g of C/100 with granule.Therefore be apparent that granularity if can prepare nanoscale LiMnPO being crucial aspect decision specific capacity and the charge/discharge rates
4Particle will improve its chemical property greatly.
Summary of the invention
The present invention proposes a kind of method that adopts sol-gel to prepare lithium ion battery material lithium manganese phosphate/carbon, its purpose is the nano level lithium manganese phosphate of synthesis of high purity, thereby improves its chemical property.
The technical solution used in the present invention is: a kind of step of the method that sol-gel prepares lithium ion battery material lithium manganese phosphate/carbon that adopts is as follows:
(1) presoma preparation: is 1.025: 1: 1 with Li source compound, manganese source compound, P source compound and complexing agent compound with mol ratio: 0-2, be dissolved in solvent or be distributed to and obtain composite material in the solvent, adopting red fuming nitric acid (RFNA) or concentrated ammonia liquor regulator solution pH value is 0.5-3.7, obtain sol solution through magnetic agitation a period of time, after treating the sol solution clarification, place it in evaporate to dryness in 60 ℃ of water-baths, until obtaining xerogel;
(2) dried: the xerogel that obtains is dry under 120 ℃, obtain dry solid, take out and obtain precursor powder through grinding;
(3) calcination process: the presoma that step (2) obtains is put into the programming rate intensification of tube furnace with 1-10 ℃/min, through 250-400 ℃ of preliminary treatment 2-6h, and under 500-700 ℃ of inert atmosphere, calcining 1-12h, naturally be cooled to room temperature, the granularity that obtains the carbon coating is the lithium manganese phosphate of 50～150nm.
Described Li source compound is selected from lithium carbonate, lithium hydroxide, lithium acetate, lithium chloride, lithium sulfate, lithium nitrate, lithium phosphate, phosphoric acid hydrogen two lithiums, lithium dihydrogen phosphate or lithium oxalate.
Described manganese source compound is selected from manganese carbonate, manganese citrate, manganese acetate, manganese dioxide, manganese dioxide or manganous hydroxide.
Described P source compound is selected from phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphorus pentoxide, phosphoric acid hydrogen two lithiums or lithium dihydrogen phosphate.
Described complexing agent compound is selected from malic acid, lactic acid, citric acid, oxalic acid, ascorbic acid, benzoic acid, malonic acid, acetate, salicylic acid, tartaric acid or their mixture.
Described solvent is selected from a kind of in water, ethanol, acetone, water-ethanol solution, ethylene glycol or the polyethylene glycol.
Described inert atmosphere is selected a kind of in nitrogen, nitrogen and hydrogen, argon gas and hydrogen or nitrogen and the argon gas mist for use, and wherein in argon gas and the hydrogen mixed gas, the volume content of hydrogen is 2～10%.
The invention has the beneficial effects as follows: this employing sol-gel prepares the method for lithium ion battery material lithium manganese phosphate/carbon, is 1.025: 1: 1 with Li source compound, manganese source compound, P source compound and complexing agent compound with mol ratio: 0-2, be dissolved in solvent or be distributed to and obtain composite material in the solvent, adopting red fuming nitric acid (RFNA) or concentrated ammonia liquor regulator solution pH value is 0.5-3.7, with solution evaporate to dryness in water-bath, get xerogel, drying and calcination process again, obtaining the granularity that carbon coats is the lithium manganese phosphate of 50～150nm.Owing to adopt xerogel preparation and control sintering condition, synthesized highly purified lithium manganese phosphate material, its energy density height, chemical property is good and stability good.This preparation method adopts xerogel to follow subsequent heat treatment, has effectively controlled the particle diameter and the chemical composition of lithium manganese phosphate, but synthesis nano lithium manganese phosphate material.By controlling heat treated temperature and time, the product crystal property is good, and the particle average grain diameter is 50～150nm, and particle diameter is little and be evenly distributed.The outside material with carbon element that coats of the active material of preparation has improved the electron conduction of lithium manganese phosphate, and has effectively stoped growing up and reuniting of particle.The synthetic lithium manganese phosphate material of this method has 4V left and right sides discharge platform, and 25 ℃, 0.02C discharge capacity first are 118.1mAh/g, have better cycle performance simultaneously.
Description of drawings
Fig. 1 is the lithium manganese phosphate X-ray diffracting spectrum of embodiment 1 preparation.
Fig. 2 is the lithium manganese phosphate sem photograph of embodiment 1 preparation.
Fig. 3 be the lithium manganese phosphate of embodiment 1 preparation under the 0.02C multiplying power, 2.0-4.5V charging and discharging curve figure.
Fig. 4 be the lithium manganese phosphate of embodiment 1 preparation under the 0.02C multiplying power, the discharge capacity cycle performance figure of 2.0-4.5V.
Fig. 5 be the lithium manganese phosphate of embodiment 1 preparation under the 0.05C-1C multiplying power, the discharge-rate performance map of 2.0-4.5V.
Embodiment
The invention will be further described below in conjunction with embodiment, can be implemented so that those skilled in the art can better understand the present invention also, but illustrated embodiment is not as a limitation of the invention.
The preparation of manganese citrate:
With manganese chloride and citric acid is raw material, 9.9g manganese chloride and 21g citric acid is dissolved in the deionized water, by the pH value to 2.7 that ammoniacal liquor comes regulator solution, magnetic agitation in 60 ℃ of water-baths.Stir about 30min, white precipitate occurs, continue stirring reaction 5h, precipitate fully up to solution, ultrasonic Treatment 30min, suction filtration obtains the manganese citrate compound.
1) presoma preparation: with 0.78g Li
2CO
3, 5.26gMn (Hct)
2, 2.3gH
3PO
4, 4.2gH (ct) 2 (Li: Mn: P: complexing agent=1.025: 1: 1: 1) be dissolved in the 100ml deionized water, stirred 10 minutes, test pH value is 3.2, obtain sol solution through magnetic agitation a period of time, after treating the sol solution clarification, place it in evaporate to dryness in 60 ℃ of water-baths, until obtaining xerogel;
2) dried: the xerogel that obtains is dry under 120 ℃, obtain dry solid, take out and obtain precursor powder through grinding;
3) calcination process: the mixture of getting after a certain amount of said process is pulverized is placed in the ceramic Noah's ark, at Ar-H
2(H wherein
2Volume fraction be 10%) adopt down the mode of temperature programming, at first the speed with 2 ℃/min is warming up to 350 ℃ of maintenance 5h with mixture, and then be heated to 550 ℃ with 5 ℃/min speed and keep 3h, naturally cool to room temperature in stove, in this process, continue in the tube furnace to feed argon hydrogen, obtain the lithium manganese phosphate that carbon coats.
Electrochemical property test is undertaken by button battery; be used for material sample that the positive pole of the button-shaped simulated battery of electric performance test makes by embodiment, conductive agent acetylene black, binding agent PVDF according to 75: 20: 5 ratio of mass ratio; making solvent with N-methyl pyrrolidone NMP is applied on the A1 paper tinsel after evenly; behind 110 ℃ of dry 2h; on the particulate tablet press machine with 15MPa pressure compressing tablet; simulated battery is assembled in the glove box of argon shield and carries out, and negative pole is a metal lithium sheet.Charge and discharge process is: carry out charge-discharge test with the 0.02C multiplying power, charging and discharging voltage is 2.0-4.5V, tests first capacity, enclosed pasture efficient and the capability retention after 20 weeks of circulating first.
The x-ray diffraction pattern of the finished-product material that embodiment 1 makes as shown in Figure 1, by knowing with the comparative analysis of standard diagram card, the material of preparation is single olivine-type LiMnPO
4, and having good degree of crystallinity, purity is higher.
Fig. 2 is prepared olivine-type LiMnPO
4The SEM of/C figure, granular size is at 50-150nm, and the sample of preparation has certain agglomeration, but agglomerated particle is uniformly dispersed, and nano-scale particle helps the diffusion of lithium ion.
Fig. 3 is LiMnPO
4The first discharge curve of/C composite material under the 0.02C multiplying power has tangible discharge platform at 4V, and the platform capacity is 60mAh/g, and discharge capacity is 118.1mAh/g first.
Fig. 4 is LiMnPO
4The cycle performance figure of/C composite material under the 0.02C multiplying power, significantly decay can appear in preceding 5 circles, though reason is that charge/discharge capacity is bigger under the low range, also can cause material structure to change simultaneously, has more serious capacitance loss under the low range and takes place.The 6th circle back decay is less, and capacity tends towards stability.After 20 circulations, discharge capacity still has 103.3mAh/g, and capability retention is 88%.
Fig. 5 is LiMnPO
4The discharge-rate performance map of/C composite material under different multiplying, capacity can reduce along with the increase of multiplying power under the different multiplying, and the 0.05C discharge capacity is 102.7mAh/g, and the 0.5C discharge capacity is 65mAh/g, and the 1C discharge capacity is 50.3mAh/g.
1) presoma preparation: with 0.78g Li
2CO
3, 5.26gMn (Hct)
2, 2.3gH
3PO
4, 4.2gH (ct) 2 (Li: Mn: P: complexing agent=1.025: 1: 1: 1) be dissolved in the 100ml deionized water, stirred 10 minutes, test pH value is 3.2, obtain sol solution through magnetic agitation a period of time, after treating the sol solution clarification, place it in evaporate to dryness in 60 ℃ of water-baths, until obtaining xerogel;
2) dried: the xerogel that obtains is dry under 120 ℃, obtain dry solid, take out and obtain precursor powder through grinding;
3) calcination process: the mixture of getting after a certain amount of said process is pulverized is placed in the ceramic Noah's ark, at Ar-H
2(H wherein
2Volume fraction be 10%) adopt down the mode of temperature programming, at first the speed with 2 ℃/min is warming up to 350 ℃ of maintenance 5h with mixture, and then be heated to 600 ℃ with 5 ℃/min speed and keep 3h, naturally cool to room temperature in stove, in this process, continue in the tube furnace to feed argon hydrogen, obtain the lithium manganese phosphate that carbon coats.
The LiMnPO for preparing with present embodiment
4/ C is through physical property test and electrochemical property test.Synthetic material is made up of the less primary particle of particle diameter, granular size is 300-400nm, particle is relatively large, itself and metal lithium sheet are done negative pole and electrode are assembled into simulated battery, with 0.02C rate charge-discharge test, charge and discharge voltage when being 2.0-4.5V, discharge capacity is 100.1mAh/g first, enclosed pasture efficient is 83.4% first, and circulation 20 circle back capability retentions are 89.7%.
1) presoma preparation: with 0.78g Li
2CO
3, 5.26gMn (Hct)
2, 2.3gH
3PO
4, 4.2gH (ct) 2 (Li: Mn: P: complexing agent=1.025: 1: 1: 1) be dissolved in the 100ml deionized water, stirred 10 minutes, test pH value is 3.2, obtain sol solution through magnetic agitation a period of time, after treating the sol solution clarification, place it in evaporate to dryness in 60 ℃ of water-baths, until obtaining xerogel;
2) dried: the xerogel that obtains is dry under 120 ℃, obtain dry solid, take out and obtain precursor powder through grinding;
3) calcination process: the mixture of getting after a certain amount of said process is pulverized is placed in the ceramic Noah's ark, at Ar-H
2(H wherein
2Volume fraction be 10%) adopt down the mode of temperature programming, at first the speed with 2 ℃/min is warming up to 350 ℃ of maintenance 5h with mixture, and then be heated to 500 ℃ with 5 ℃/min speed and keep 3h, naturally cool to room temperature in stove, in this process, continue in the tube furnace to feed argon hydrogen, obtain the lithium manganese phosphate that carbon coats.
The LiMnPO for preparing with present embodiment
4/ C is through physical property test and electrochemical property test.Synthetic material is made up of the less primary particle of particle diameter, granular size is 100-300nm, particle is bigger, agglomeration is arranged, and itself and metal lithium sheet are done negative pole and electrode are assembled into simulated battery, test with the 0.02C rate charge-discharge, charge and discharge voltage when being 2.0-4.5V, discharge capacity is 54.1mAh/g first, and enclosed pasture efficient is 71.4% first, and circulation 20 circle back capability retentions are 94.3%.
1) presoma preparation: with 0.78g Li
2CO
3, 5.26gMn (Hct)
2, 2.3gH
3PO
4, 4.2gH (ct) 2 (Li: Mn: P: complexing agent=1.025: 1: 1: 1) be dissolved in the 100ml deionized water, adopting red fuming nitric acid (RFNA) or concentrated ammonia liquor regulator solution pH value is 0.5, obtain sol solution through magnetic agitation a period of time, after treating the sol solution clarification, place it in evaporate to dryness in 60 ℃ of water-baths, until obtaining xerogel;
2) dried: the xerogel that obtains is dry under 120 ℃, obtain dry solid, take out and obtain precursor powder through grinding;
3) calcination process: the mixture of getting after a certain amount of said process is pulverized is placed in the ceramic Noah's ark, at Ar-H
2(H wherein
2Volume fraction be 10%) adopt down the mode of temperature programming, at first the speed with 2 ℃/min is warming up to 350 ℃ of maintenance 5h with mixture, and then be heated to 550 ℃ with 5 ℃/min speed and keep 3h, naturally cool to room temperature in stove, in this process, continue in the tube furnace to feed argon hydrogen, obtain the lithium manganese phosphate that carbon coats.
The LiMnPO for preparing with present embodiment
4/ C is through physical property test and electrochemical property test.Synthetic material is made up of the less primary particle of particle diameter, granular size is 100-300nm, particle is relatively large, itself and metal lithium sheet are done negative pole and electrode are assembled into simulated battery, with 0.02C rate charge-discharge test, charge and discharge voltage when being 2.0-4.5V, discharge capacity is 79.0mAh/g first, enclosed pasture efficient is 79.8% first, and circulation 20 circle back capability retentions are 102.4%.
1) presoma preparation: with 0.78g Li
2CO
3, 5.26gMn (Hct)
2, 2.3gH
3PO
4, 4.2gH (ct) 2 (Li: Mn: P: complexing agent=1.025: 1: 1: 1) be dissolved in the 100ml deionized water, adopting red fuming nitric acid (RFNA) or concentrated ammonia liquor regulator solution pH value is 3.7, obtain sol solution through magnetic agitation a period of time, after treating the sol solution clarification, place it in evaporate to dryness in 60 ℃ of water-baths, until obtaining xerogel;
2) dried: the xerogel that obtains is dry under 120 ℃, obtain dry solid, take out and obtain precursor powder through grinding;
3) calcination process: the mixture of getting after a certain amount of said process is pulverized is placed in the ceramic Noah's ark, at Ar-H
2(H wherein
2Volume fraction be 10%) adopt down the mode of temperature programming, at first the speed with 2 ℃/min is warming up to 350 ℃ of maintenance 5h with mixture, and then be heated to 550 ℃ with 5 ℃/min speed and keep 3h, naturally cool to room temperature in stove, in this process, continue in the tube furnace to feed argon hydrogen, obtain the lithium manganese phosphate that carbon coats.
The LiMnPO for preparing with present embodiment
4/ C is through physical property test and electrochemical property test.Synthetic material is made up of the less primary particle of particle diameter, granular size is 40-130nm, particle is less relatively, serious agglomeration is arranged, and be agglomerated into the bulk particle, itself and metal lithium sheet are done negative pole and electrode are assembled into simulated battery, with 0.02C rate charge-discharge test, charge and discharge voltage when being 2.0-4.5V, discharge capacity is 65.7mAh/g first, enclosed pasture efficient is 81.3% first, and circulation 20 circle back capability retentions are 106.5%.
1) presoma preparation: with 0.78g Li
2CO
3, 5.26gMn (Hct)
2, 2.3gH
3PO
4, 2.1gH (ct) 2 (Li: Mn: P: complexing agent=1.025: 1: 1: 0) be dissolved in the 100ml deionized water, stirred 10 minutes, the test pH value is 3.0, obtain sol solution through magnetic agitation a period of time, after treating the sol solution clarification, place it in evaporate to dryness in 60 ℃ of water-baths, until obtaining xerogel;
2) dried: the xerogel that obtains is dry under 120 ℃, obtain dry solid, take out and obtain precursor powder through grinding;
3) calcination process: the mixture of getting after a certain amount of said process is pulverized is placed in the ceramic Noah's ark, at Ar-H
2(H wherein
2Volume fraction be 10%) adopt down the mode of temperature programming, at first the speed with 2 ℃/min is warming up to 350 ℃ of maintenance 5h with mixture, and then be heated to 550 ℃ with 5 ℃/min speed and keep 3h, naturally cool to room temperature in stove, in this process, continue in the tube furnace to feed argon hydrogen, obtain the lithium manganese phosphate that carbon coats.
The LiMnPO for preparing with present embodiment
4/ C is through physical property test and electrochemical property test.Synthetic material is made up of the less primary particle of particle diameter, granular size is 400-600nm, particle is relatively large, itself and metal lithium sheet are done negative pole and electrode are assembled into simulated battery, with 0.02C rate charge-discharge test, charge and discharge voltage when being 2.0-4.5V, discharge capacity is 57.7mAh/g first, enclosed pasture efficient is 71.6% first, and circulation 20 circle back capability retentions are 88%.
1) presoma preparation: with 0.78g Li
2CO
3, 5.26gMn (Hct)
2, 2.3gH
3PO
4, 8.4gH (ct) 2 (Li: Mn: P: complexing agent=1.025: 1: 1: 2) be dissolved in the 100ml deionized water, stirred 10 minutes, test pH value is 3.0, obtain sol solution through magnetic agitation a period of time, after treating the sol solution clarification, place it in evaporate to dryness in 60 ℃ of water-baths, until obtaining xerogel;
2) dried: the xerogel that obtains is dry under 120 ℃, obtain dry solid, take out and obtain precursor powder through grinding;
3) calcination process: the mixture of getting after a certain amount of said process is pulverized is placed in the ceramic Noah's ark, at Ar-H
2(H wherein
2Volume fraction be 10%) adopt down the mode of temperature programming, at first the speed with 2 ℃/min is warming up to 350 ℃ of maintenance 5h with mixture, and then be heated to 550 ℃ with 5 ℃/min speed and keep 3h, naturally cool to room temperature in stove, in this process, continue in the tube furnace to feed argon hydrogen, obtain the lithium manganese phosphate that carbon coats.
The LiMnPO for preparing with present embodiment
4/ C is through physical property test and electrochemical property test.Synthetic material is made up of the less primary particle of particle diameter, granular size is 30-120nm, there is obvious reunion existing, itself and metal lithium sheet are done negative pole and electrode are assembled into simulated battery, with the test of 0.02C rate charge-discharge, when charging and discharging voltage 2.0-4.5V, discharge capacity is 74.8mAh/g first, enclosed pasture efficient is 75.3% first, and circulation 20 circle back capability retentions are 99.6%.
By the foregoing description 1-7 as seen, the present invention successfully synthesizes highly purified lithium manganese phosphate positive electrode material, discharge platform with 4V, platform is longer, and prepared positive electrode has higher discharge capacity, can reach 118.1mAh/g, 20 circulations, capability retention is 88%, and cycle performance is better.In a word,, significantly improved the chemical property of material,, had great help the study on the synthesis of lithium ion battery anode material manganese lithium phosphate by the optimization of condition.
Claims (7)
1. method that adopts sol-gel to prepare lithium ion battery material lithium manganese phosphate/carbon, it is characterized in that: the step of this method is as follows:
(1) presoma preparation: is 1.025: 1: 1 with Li source compound, manganese source compound, P source compound and complexing agent compound with mol ratio: 0-2, be dissolved in solvent or be distributed to and obtain composite material in the solvent, adopting red fuming nitric acid (RFNA) or concentrated ammonia liquor regulator solution pH value is 0.5-3.7, obtain sol solution through magnetic agitation a period of time, after treating the sol solution clarification, place it in evaporate to dryness in 60 ℃ of water-baths, until obtaining xerogel;
(2) dried: the xerogel that obtains is dry under 120 ℃, obtain dry solid, take out and obtain precursor powder through grinding;
(3) calcination process: the presoma that step (2) obtains is put into the programming rate intensification of tube furnace with 1-10 ℃/min, through 250-400 ℃ of preliminary treatment 2-6h, and under 500-700 ℃ of inert atmosphere, calcining 1-12h, naturally be cooled to room temperature, the granularity that obtains the carbon coating is the lithium manganese phosphate of 50～150nm.
2. employing sol-gel according to claim 1 prepares the method for lithium ion battery material lithium manganese phosphate/carbon, it is characterized in that: described Li source compound is selected from lithium carbonate, lithium hydroxide, lithium acetate, lithium chloride, lithium sulfate, lithium nitrate, lithium phosphate, phosphoric acid hydrogen two lithiums, lithium dihydrogen phosphate or lithium oxalate.
3. employing sol-gel according to claim 1 prepares the method for lithium ion battery material lithium manganese phosphate/carbon, it is characterized in that: described manganese source compound is selected from manganese carbonate, manganese citrate, manganese acetate, manganese dioxide, manganese dioxide or manganous hydroxide.
4. employing sol-gel according to claim 1 prepares the method for lithium ion battery material lithium manganese phosphate/carbon, it is characterized in that: described P source compound is selected from phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphorus pentoxide, phosphoric acid hydrogen two lithiums or lithium dihydrogen phosphate.
5. employing sol-gel according to claim 1 prepares the method for lithium ion battery material lithium manganese phosphate/carbon, it is characterized in that: described complexing agent compound is selected from malic acid, lactic acid, citric acid, oxalic acid, ascorbic acid, benzoic acid, malonic acid, acetate, salicylic acid, tartaric acid or their mixture.
6. employing sol-gel according to claim 1 prepares the method for lithium ion battery material lithium manganese phosphate/carbon, it is characterized in that: described solvent is selected from a kind of in water, ethanol, acetone, water-ethanol solution, ethylene glycol or the polyethylene glycol.
7. employing sol-gel according to claim 1 prepares the method for lithium ion battery material lithium manganese phosphate/carbon, it is characterized in that: described inert atmosphere is selected a kind of in nitrogen, nitrogen and hydrogen, argon gas and hydrogen or nitrogen and the argon gas mist for use, wherein in argon gas and the hydrogen mixed gas, the volume content of hydrogen is 2～10%.
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| CN102709554A (en) * | 2012-02-22 | 2012-10-03 | 上海大学 | LiMnPO4/C composite cathode material preparation method for lithium ion battery |
| CN102769138A (en) * | 2012-08-07 | 2012-11-07 | 天津优量锂能科技有限公司 | Method for synthesizing manganese phosphate lithium sol-gel doped with other metal ions |
| CN103413940A (en) * | 2013-07-22 | 2013-11-27 | 上海应用技术学院 | Synthetic method for cathode material nano lithium manganese phosphate for lithium ion batteries |
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| CN108054347A (en) * | 2017-10-09 | 2018-05-18 | 南京航空航天大学 | A kind of nano lithium manganese phosphate of lithium/carbon positive electrode and preparation method thereof |
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| CN111167443A (en) * | 2020-01-20 | 2020-05-19 | 武汉大学 | Novel ruthenium-based catalyst and preparation method and application thereof |
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| CN102709554A (en) * | 2012-02-22 | 2012-10-03 | 上海大学 | LiMnPO4/C composite cathode material preparation method for lithium ion battery |
| CN102709554B (en) * | 2012-02-22 | 2014-10-15 | 上海大学 | LiMnPO4/C composite cathode material preparation method for lithium ion battery |
| CN102633250A (en) * | 2012-03-29 | 2012-08-15 | 天津巴莫科技股份有限公司 | High-voltage anode material for lithium ion batteries and method for preparing high-voltage anode material |
| CN102769138A (en) * | 2012-08-07 | 2012-11-07 | 天津优量锂能科技有限公司 | Method for synthesizing manganese phosphate lithium sol-gel doped with other metal ions |
| CN103413940A (en) * | 2013-07-22 | 2013-11-27 | 上海应用技术学院 | Synthetic method for cathode material nano lithium manganese phosphate for lithium ion batteries |
| CN103413940B (en) * | 2013-07-22 | 2015-10-28 | 上海应用技术学院 | A kind of synthetic method of positive material nano lithium manganese phosphate of lithium ion battery |
| CN106935832A (en) * | 2017-03-31 | 2017-07-07 | 四川浩普瑞新能源材料股份有限公司 | Lithium manganese phosphate composite, its preparation method and lithium ion battery |
| CN108054347A (en) * | 2017-10-09 | 2018-05-18 | 南京航空航天大学 | A kind of nano lithium manganese phosphate of lithium/carbon positive electrode and preparation method thereof |
| CN110854384A (en) * | 2019-11-26 | 2020-02-28 | 河北省科学院能源研究所 | Preparation method of surface-modified nickel-based electrode material |
| CN110854384B (en) * | 2019-11-26 | 2021-04-02 | 河北省科学院能源研究所 | Preparation method of surface-modified nickel-based electrode material |
| CN111224103A (en) * | 2020-01-17 | 2020-06-02 | 贝特瑞（天津）纳米材料制造有限公司 | Preparation method of metal ion-doped high-rate mesoporous lithium iron phosphate cathode material |
| CN111167443A (en) * | 2020-01-20 | 2020-05-19 | 武汉大学 | Novel ruthenium-based catalyst and preparation method and application thereof |
| CN112174214A (en) * | 2020-08-17 | 2021-01-05 | 安徽绿沃循环能源科技有限公司 | Lithium battery LiMn2O4Preparation method of positive electrode material |
| CN113782731A (en) * | 2021-08-20 | 2021-12-10 | 中南大学 | Cathode material for water-based zinc secondary battery and preparation method thereof |
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