CN102074680A - Method for composing anode materials of secondary lithium ion battery - Google Patents
Method for composing anode materials of secondary lithium ion battery Download PDFInfo
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- CN102074680A CN102074680A CN2010101943245A CN201010194324A CN102074680A CN 102074680 A CN102074680 A CN 102074680A CN 2010101943245 A CN2010101943245 A CN 2010101943245A CN 201010194324 A CN201010194324 A CN 201010194324A CN 102074680 A CN102074680 A CN 102074680A
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- Y02E60/10—Energy storage using batteries
Abstract
The present invention discloses a method and system for composing anode materials of secondary lithium ion battery. The method comprises: mixing a raw material precursor lithium-contained compound, a metal M-contained compound and a phosphorus-contained compound according to a stoichiometric ratio and grinding the compounds to be mixed materials; burning the mixed material by chemical gas phase reduction method to obtain LiMPO4/C composite material. The method of the present invention has the advantages of easy operation, strong controllability high repeatability and energy conversation and the like. The present invention further provides LiMPO4/C composite material obtained by the method and electrode and batteries containing the composite material.
Description
Technical field
The present invention relates to the method for synthetic secondary lithium battery positive electrode.More specifically, the present invention relates to synthesize the LiMPO that carbon coats with the chemical gaseous phase reduction
4Method, wherein M is transition metal or its combination that is selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn.
Background technology
It is found that the TiS that can embed lithium ion since the seventies
2After the metallic compound, secondary lithium battery becomes one of battery technology of speed with fastest developing speed, is widely used in such as portable electric appts such as mobile phone, notebook computer, video cameras.Be applied to aspect electric automobile and the hybrid vehicle, lithium ion battery also has great potential.
Lithium ion battery generally includes the electrolyte between negative pole, positive pole and the both positive and negative polarity.The nineties in 20th century, SONY adopted cobalt acid lithium to do positive electrode, and graphite is done negative material.Up to the present, the commercial Li-ion batteries majority is still done positive electrode with cobalt acid lithium or lithium nickel cobalt dioxide, but because the cobalt resource scarcity, cost an arm and a leg, shortcoming such as contaminated environment, people also attempt to seek better positive electrode material compound always.
1997, the olivine-type LiFePO that people such as Goodenough propose
4Positive electrode caused people pay close attention to greatly (United States Patent (USP) NO.5,910,382 and 6,514,640B1).LiFePO
4Positive electrode is owing to have advantages such as theoretical capacity height (170mAh/g), raw material sources be abundant, cheap, safe, environmentally friendly, thereby is considered to the first-selected positive electrode of power lithium-ion battery of new generation.Yet, although LiFePO
4Positive electrode has above-mentioned multiple advantage, but its extremely low electronic conductivity and lithium ion diffusion coefficient had a strong impact on its chemical property particularly multiplying power charge and discharge performance, thereby the commerce that has limited this material is used.Carry out a lot of researchs and improved LiFePO
4The chemical property of positive electrode, these researchs mainly concentrate on two kinds of approach, the first improves the electron conduction of positive electrode itself by foreign cation, its two be synthesize granularity little comprise nano level LiFePO
4And/or add conductive additive for example carbon or metal dust.Reported that multiple route of synthesis synthesizes the LiFePO of small grain size and carbon coating
4For example solution-gel method, coprecipitation, hydro thermal method or the like, the carbon source of using comprises for example (A PVB-basedrheological phase approach to nano-LiFePO4/C composite cathodes such as sucrose, PVA, benzene of elemental carbon or organic carbon source, Hui Liu etal.Powder Technology, 184 (2008) 313-317).
At present, the main manufacturer of lithium ion battery adopts carbothermic method to produce LiFePO
4, with FeC
2O
4+ Li
2CO
3+ NH
4H
2PO
4, Fe
2O
3+ LiH
2PO
4Or Li
2CO
3+ FePO
4Be raw material, in course of reaction, add elemental carbon or organic carbon source etc. (U.S. Patent No. 7,060,206B2 and 7,276,218B2) and be reflected at such as the inert gas of argon gas or and/or such as or the reducibility gas of hydrogen in carry out.The carbon that adds mainly plays three effects, and (1) as conductive additive or conductive additive precursor, wherein organic carbon decomposes the generation carbon black, and carbon black is usually as conductive additive; (2) when the Fe precursor be Fe
3+The time, be used as reducing agent with Fe
3+Be converted into Fe
2+(3) prevent Fe
2+The trace dioxygen oxidation that is existed in the inert atmosphere.
Publication number is that the Chinese patent application of CN101237039A discloses the synthetic LiFePO of a kind of based on chemical gas phase sediment auxiliary solid phase
4The method of/C material, course of reaction are divided into precalcining and final two stages of calcining, have wherein used organic precursor for example glucose, sucrose, benzene etc., and the precalcining step is carried out in inert gas.
Publication number is that the Chinese patent application of CN1478310A is used FePO
42H
2O and Li
2CO
3Prepared in reaction LiFePO
4, and compared the LiFePO of preparation like this
4LiFePO with other coating carbon
4, reactions all in the disclosure content are all carried out in reproducibility and/or inert gas.
In sum, this area still needs to synthesize the LiFePO with excellent electrochemical properties
4The method that positive electrode and controllability are strong, repeatability is high, easy and simple to handle, save energy.
Summary of the invention
The present invention has satisfied above-mentioned and other demand by the method that a kind of synthetic secondary lithium battery positive electrode is provided.
In one aspect of the invention, provide a kind of synthetic LiMPO
4The method of/C composite material, wherein M is metal or its combination that is selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn, this method may further comprise the steps:
1) by compound and phosphorus-containing compound mixing and the grinding of stoichiometric proportion, to obtain compound with lithium-containing compound, containing metal M;
2) with the chemical gaseous phase reducing process described compound is calcined to obtain LiMPO
4/ C composite material.
Aspect another, provide the LiMPO that obtains according to the inventive method in the present invention
4/ C composite material, wherein M is metal or its combination that is selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn, described LiMPO
4The average grain diameter of/C composite material is in 0.02 μ m to 1.0 mu m range, and carbon-coating thickness is in 0.001 to 0.1 mu m range.
, provide to contain the LiMPO that with good grounds the inventive method obtains aspect another in the present invention
4The electrode of/C composite material.
, provide to contain the LiMPO that with good grounds the inventive method obtains aspect another in the present invention
4The battery of/C composite material.
Synthetic method according to the present invention has multiple advantage, for example comprises, a. has used for example MPO of high valence state slaine
4The precalcining step is not added elemental carbon or organic carbon source, so precalcining can carry out under air conditions, even can omit this precalcining step, compare conventional technology of under inert atmosphere, carrying out precalcining, saved the cost of inert gas in the precalcining step and/or reducibility gas; B. owing to can only use two kinds of raw material precursors, therefore make the easier dispersion of raw material in the process of lapping, course of reaction also has higher controllability and repeatability; C. FeC commonly used with respect to this area
2O
4+ Li
2CO
3+ NH
4H
2PO
4Method, in the reactions steps involved in the present invention, do not have any NH
3Therefore gas purging does not need NH
3Carry out reprocessing, cost is lower, more environmental protection; D compares with current commercially available prod, and the positive electrode that obtains with the inventive method has suitable or better chemical property.
Description of drawings
Fig. 1 is to use the X-ray powder diffraction collection of illustrative plates (XRPD) of the LiFePO 4 material of the inventive method preparation.
Fig. 2 shows the LiFePO that obtains with the inventive method
4Material (Fig. 2 A) and commercially available several main LiFePO
4The capacitance of product (Fig. 2 B-2D) relatively.
Fig. 3 shows the LiFePO that obtains with the inventive method
4Material (Fig. 3 A) and commercially available several main LiFePO
4The comparison of the cycle period of product (Fig. 3 B-3D).
Fig. 4 shows the LiFePO that obtains with the inventive method
4Material (Fig. 4 A) and a kind of commercially available LiFePO
4The multiplying power of product (Fig. 4 B) charges and discharge the comparison (Fig. 4 C) of performance.The LiFePO that " HON " expression obtains with the inventive method
4Sample.
Fig. 5 shows the LiFePO that obtains with the inventive method
4Material (Fig. 5 A, left figure scale are 10 μ m, and right figure scale is 1 μ m) and a kind of commercially available LiFePO
4The fineness ratio of product (Fig. 5 B, left figure scale are 10 μ m, and right figure scale is 1 μ m).
Fig. 6 shows the LiFePO that obtains with the inventive method
4Material (Fig. 6 A) and present two kinds of commercially available LiFePO
4The fineness ratio of product (Fig. 6 B and Fig. 6 C).
Fig. 7 shows the LiFePO that obtains with the inventive method
4The carbon-coating that coats on the material, wherein Fig. 7 A scale is 0.5 μ m, Fig. 7 B scale is 20nm.
Embodiment
The present invention is based on following discovery: use the chemical gaseous phase reduction technique, can be implemented in and do not add carbon or organic carbon source in the reaction raw materials, and under the condition that does not have inertia and/or reducibility gas, carry out precalcining and maybe can omit the precalcining step, only by in calcining step, utilizing the chemical gaseous phase reduction technique, and realize that simultaneously carbon is coated with synthesis of anode material of lithium-ion battery LiMPO with raw material precursor reduction
4, include but not limited to LiFePO
4
In one aspect of the invention, provide a kind of synthetic LiMPO
4The method of/C composite material, wherein M is metal or its combination that is selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn, this method may further comprise the steps: by compound and phosphorus-containing compound mixing and the grinding of stoichiometric proportion with lithium-containing compound, containing metal M, to obtain compound; And, with the chemical gaseous phase reducing process described compound is calcined to obtain LiMPO
4/ C composite material.
The raw material precursor that uses in the inventive method comprises compound and the phosphorus-containing compound of lithium-containing compound, containing metal M.For example, lithium-containing compound can be selected from one or more in lithium carbonate, lithium chloride, lithium acetate, lithium sulfate, lithium nitrate, lithium hydroxide, lithium phosphate, lithium dihydrogen phosphate, phosphoric acid hydrogen two lithiums and the lithium oxalate.The compound of containing metal M can be selected from one or more in phosphate, carbonate, oxalates, sulfate, hydroxide or the oxide of metal M.Phosphorus-containing compound can be selected from one or more in metal phosphate, ammonium phosphate and the phosphoric acid, and wherein metal phosphate can be the phosphate of metal M or the phosphate of other metals.In a kind of preferred implementation, lithium-containing compound is Li
2CO
3, metal M is that compound and the phosphorus-containing compound of Fe and containing metal M is FePO
4In another kind of preferred implementation, metal M has variable valency, for example divalence and trivalent, and preferably M has for example trivalent of high valence state in as the compound of the containing metal M of raw material precursor.For example when M is iron, use ferric iron in the preferred feedstock precursor, for example FePO
4
In the methods of the invention, can be earlier with the raw material precursor mixing of stoichiometric proportion, for example the stoichiometric proportion of Li, Fe and P is 1: 1: 1.A kind of preferred embodiment in, when the raw material precursor is Li
2CO
3And FePO
4During two kinds of compounds, can utilize 1: 2 Li of mol ratio
2CO
3And FePO
4Produce LiFePO
4
In some embodiments, step 2) middle temperature of calcining is in 500-800 ℃ of scope, and for example calcining heat can be selected from 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃ and 800 ℃ or its any combination.In some preferred implementation, calcining heat in 600-800 ℃ or 650-750 ℃ of scope, preferred 650 ℃.Described calcining can be calcining at constant temperature, for example 650 ℃ of calcining at constant temperature.
In some embodiments, step 2) time of calcining is 5-48 hour in, and for example calcination time is selected from 5,10,15,20,25,30,35,40,45 and 48 hours, preferred 5-20 hour.For example, 650 ℃ of calcining at constant temperature are 10 hours.
LiMPO
4Can contain more than one for example cations of two kind of first row transition metal in the positive electrode.Some preferred embodiment in, LiMPO
4Be selected from LiFe
1-xTi
xPO
4, LiFe
1-xV
xPO
4, LiFe
1-xCr
xPO
4, LiFe
1-xMn
xPO
4, LiFe
1-xCo
xPO
4And LiFe
1-xNi
xPO
4, 0≤X≤1 wherein.In further preferred embodiment, LiMPO
4Be LiFePO
4Contain in positive electrode of the present invention under the situation of the transition-metal cation outside the deironing, those skilled in the art should be able to use the temperature and time of Ellingham curve adjustment calcining to obtain required product.
Used chemical gaseous phase reducing process can be described as by using carrier gas that organic substance is blown in the reacting furnace among the present invention, by organic substance reduction at high temperature, reaches the purpose of synthetic end product.Calcining of the present invention can be carried out under the vapour phase reduction condition, promptly uses carrier gas to be blown in the reacting furnace organic substance and calcining.The chemical gaseous phase reducing process can use routine techniques well known to those skilled in the art and equipment to carry out.Chemical gaseous phase reduction carrier gas can include but not limited to nitrogen, argon gas and helium for inert gas, also can include but not limited to hydrogen, acetylene and ethene for reducibility gas.Among the present invention, chemical gaseous phase is reduced employed organic compound and is lower than 100 ℃ stable organic compound for saturated vapour pressure at ambient temperature greater than boiling point under the stable organic compound of 133.32Pa (0.1mmHg) or the normal pressure, and for example described organic compound can be selected from one or more in toluene, benzene, styrene, dimethylbenzene, biphenyl, naphthalene, anthracene, phenanthrene, ethanol, acetonitrile, ethyl acetate, propyl alcohol, acetone, propylene glycol, the butanone.
The grinding of raw material can use this area routine to be used for any suitable device with raw material pulverizing, for example ball mill, more preferably planetary ball mill in the inventive method.Can adopt dry grinding, maybe can add solvent and carry out wet grinding.The chemical gaseous phase reduction can for example be carried out in the LiFePO4 synthesis device of routine.
The inventive method can comprise or not comprise the precalcining step.Before high-temperature calcination, carry out precalcining in some execution mode, for example in 200-500 ℃ of scope, preferred 300-400 ℃, most preferably 400 ℃, precalcining 1 to 10 hour, preferred 3-8 hour, more preferably 4-7 hour, for example 5 hours.In this embodiment, additionally do not add reducing agent for example carbon or organic carbon source in the precalcining, so precalcining can be carried out in air and not need inertia and/or reducing atmosphere.In the other execution mode, method of the present invention does not comprise the precalcining step, and the raw material precursor is mixed directly calcining of back, for example, and such as 500-800 ℃ high-temperature calcination.
The method according to this invention, can also adjust the ratio of lithium and the preferred iron of transition metal in the raw material, thereby optimize the micro-structural, pattern and the thickness that for example are coated on the carbon-coating on the lithium ion anode material, and then optimize the chemical property that end-product is the lithium ion anode material of carbon coating.
Therefore, in one embodiment, the invention provides a kind of synthetic LiFePO
4The method of/C composite material may further comprise the steps: press Li: Fe: the stoichiometric proportion of P 1: 1: 1 is with Li
2CO
3And FePO
4Mix and grinding, to obtain compound; With the chemical gaseous phase reducing process with described compound for example 500-800 ℃ of calcining to obtain LiFePO
4/ C composite material.This method does not comprise the precalcining step, but can obtain to carry out precalcining behind the compound in some embodiments yet, for example calcines 5 hours for 400 ℃.In the precalcining process, do not add carbon or organic carbon source, and precalcining can carry out in air, not need inertia or reducing atmosphere.With chemical gaseous phase reducing process calcined mixed material the time, available nitrogen is blown into toluene in the reacting furnace as carrier gas, at high temperature ferric iron is reduced to ferrous iron, and carbon-coating is coated on LiFePO
4On.In this embodiment, each reaction condition for example calcines and the optimum condition of time of precalcining (if any), temperature, carrier gas etc. can be with reference to preamble.
In the method for the present invention not at raw material precursor Li for example
2CO
3And MPO
4Middle extra reducing agent for example elemental carbon or the organic carbon source of adding, need in inertia and/or reducing atmosphere, not carry out precalcining yet, therefore with respect to this area conventional method, the controllability of the inventive method, repeatability and operability are higher, and shown in Fig. 2-7, the LiFePO that the inventive method obtains
4Sample and commercially available several main LiFePO
4Product is compared to have suitable even more excellent chemical property.
The major parameter of assessment li-ion electrode materials comprises that capacitance, cycle life, multiplying power charge and discharge performance, granularity and conductance etc.Capacitance is the energy that the 1g material can store, and uses the electrode material of high-capacitance can make the battery operated long time.LiFePO
4Capacitance generally greater than 130mAh/g.As shown in Figure 2, the LiFePO that produces with the inventive method
4The capacitance of sample (Fig. 2 A) is 131mAh/g, with present obtainable LiFePO
4Capacitance is suitable even better.
Cycle life refers in specific loss of capacitance scope the charge/discharge number of times that (normally 80%) carried out, and uses the electrode material that has extended cycle life can make the useful life of battery longer, and then reduces client's use cost.LiFePO
4Cycle life can be greater than 2000 times.As shown in Figure 3, the LiFePO that produces with the inventive method
4Sample (Fig. 3 A) only has 1% loss of capacitance after 50 circulations.
Multiplying power charges and discharge the speed that performance refers to that electrode material can be recharged or discharge.Multiplying power charges and discharge the charge or discharge in the short period of time of well behaved electrode material.Because LiFePO
4The character that material is intrinsic, its multiplying power charges and discharge poor-performing.As shown in Figure 4, according to LiFePO of the present invention
4Sample has more excellent multiplying power and charges and discharge performance.
LiFePO
4The granularity of material is directly related with surface area.Granule helps obtaining preferably that multiplying power charges and discharge performance, but bulky grain helps obtaining bigger energy content of battery density, therefore to LiFePO
4The bigger secondary granule that material preferably is made up of less primary granule.As shown in Figure 5 and Figure 6, according to LiFePO of the present invention
4Sample has suitable primary granule and secondary granule size, therefore provides possibility for obtaining excellent chemical property.
Fig. 7 has shown LiFePO of the present invention
4The carbon-coating that coats on the sample.By finding out among the figure that carbon-coating is evenly distributed.
The ability of electron gain when conductivity is represented electrode discharge.High conductivity helps multiplying power and charges and discharge performance.According to LiFePO of the present invention
4The sample conductivity is 10
-3S/cm is significantly higher than pure LiFePO
4Conductivity, also be higher than the conductivity of commercially available prod.
Embodiment
Embodiment 1
Press chemical dosage ratio Li: Fe: P=1: 1: 1, take by weighing Li
2CO
3And FePO
42H
2O (available from Aldrich) evenly mixes to be incorporated in to grind on the planetary ball mill that goes at express speed to make it to mix in 4 hours becomes powder.This powder is changed in the Muffle furnace 400 ℃ of precalcinings 4 hours then.Then the powder transfer that precalcining is obtained to the tube furnace with 5 ℃/minute heating rate heating, after treating that temperature rises to 650 ℃, with high purity nitrogen is that carrier gas is blown into organic substance toluene in the tube furnace, 650 ℃ of calcining at constant temperature 10 hours, obtains LiFePO behind the natural cooling
4The positive electrode sample.
Use the structure of X-ray powder diffraction confirmation sample, as shown in Figure 1.
The isoparametric measurement of conductivity is by this area conventional method.
After testing, the capacitance of above-mentioned gained sample is about 131mAh/g, and cycle life is the capacitance of 50 circulation losses about 1%, and conductivity is about 10
-3S/cm, chemical property and main commercially available prod are quite or be better than commercially available prod (Fig. 2-4).
Embodiment 2-8
The operation of these embodiment is similar to Example 1, continues 20 hours, 700 ℃ and continues 10 hours, 750 ℃ and continue 5 hours, 750 ℃ and continue 10 hours, 750 ℃ and continue 48 hours, 800 ℃ and continue 10 hours but calcining continues 10 hours, 650 ℃ at 500 ℃ respectively.The LiFePO that obtains
4Sample confirms structure through X-ray powder diffraction.The performance of sample is similar to Example 1.
Embodiment 9
Press chemical dosage ratio Li: Fe: P=1: 1: 1, take by weighing Li
2CO
3And FePO
42H
2O (available from Aldrich) evenly mixes to be incorporated in to grind on the planetary ball mill that goes at express speed to make it to mix in 4 hours becomes powder.Then with this powder transfer to the tube furnace with 5 ℃/minute heating rate heating, treat that temperature rises to 650 ℃ after, be that carrier gas is blown into organic substance toluene in the tube furnace with high purity nitrogen, 650 ℃ of calcining at constant temperature 10 hours, obtain LiFePO behind the natural cooling
4The positive electrode sample.The LiFePO that obtains
4Sample confirms structure through X-ray powder diffraction.The performance of this sample is similar to Example 1.
Embodiment 10-16
The operation of these embodiment is similar to Example 9, continues 20 hours, 700 ℃ and continues 10 hours, 750 ℃ and continue 5 hours, 750 ℃ and continue 10 hours, 750 ℃ and continue 48 hours, 800 ℃ and continue 10 hours but calcining continues 10 hours, 650 ℃ at 500 ℃ respectively.The LiFePO that obtains
4Sample confirms structure through X-ray powder diffraction.The performance of sample is similar to Example 1.
The description of the above-mentioned execution mode of the present invention for explaination and illustrative purposes, is not to limit the present invention by any way only.Clearly, those skilled in the art can much change and change according to the instruction of the context of the invention.These changes and changing in the spirit and scope of the invention all drop on claim and limited.
Claims (18)
1. synthetic LiMPO
4The method of/C composite material, wherein M is metal or its combination that is selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn, this method may further comprise the steps:
1) by compound and phosphorus-containing compound mixing and the grinding of stoichiometric proportion, to obtain compound with lithium-containing compound, containing metal M;
2) with the chemical gaseous phase reducing process described compound is calcined to obtain LiMPO
4/ C composite material.
2. the method for claim 1, wherein said lithium-containing compound is selected from one or more in lithium carbonate, lithium chloride, lithium acetate, lithium sulfate, lithium nitrate, lithium hydroxide, lithium phosphate, lithium dihydrogen phosphate, phosphoric acid hydrogen two lithiums and the lithium oxalate; The compound of described containing metal M is selected from one or more in phosphate, carbonate, oxalates, sulfate, hydroxide or the oxide of metal M; Described phosphorus-containing compound is selected from one or more in metal phosphate, ammonium phosphate and the phosphoric acid.
3. method as claimed in claim 2, wherein said lithium-containing compound is Li
2CO
3, metal M is that compound and the phosphorus-containing compound of Fe and containing metal M is FePO
4
4. the method for claim 1, wherein metal M have variable valency and in the compound of containing metal M M be in high valence state.
5. the method for claim 1, wherein LiMPO
4Be selected from LiFe
1-xTi
xPO
4, LiFe
1-xV
xPO
4, LiFe
1-xCr
xPO
4, LiFe
1-xMn
xPO
4, LiFe
1-xCo
xPO
4, and LiFe
1-xNi
xPO
4, 0≤X≤1 wherein.
6. method according to any one of the preceding claims, wherein step 2) in calcining heat in 500-800 ℃ of scope.
7. method as claimed in claim 6, wherein said calcining heat is in 650-750 ℃ of scope.
8. method as claimed in claim 6, wherein said calcining heat are selected from 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃ and 800 ℃ or its any combination.
9. method according to any one of the preceding claims, wherein step 2) in calcination time in 5-48 hour scope.
10. method as claimed in claim 9, wherein said calcination time is selected from 5,10,15,20,25,30,35,40,45 and 48 hours.
11. method according to any one of the preceding claims is wherein in step 1) and step 2) between also comprise the precalcining step, this precalcining step was included in the 200-500 ℃ of scope calcining 1-10 hour.
12. method according to any one of the preceding claims, wherein step 2) the chemical gaseous phase reducing process comprise and use carrier gas that organic compound is blown in the reacting furnace.
13. method as claimed in claim 12, wherein said carrier gas be selected from nitrogen, argon gas and the helium one or more inert gas or be selected from one or more reducibility gas in hydrogen, acetylene and the ethene.
14. method as claimed in claim 12, wherein said organic compound is lower than 100 ℃ stable organic compound for saturated vapour pressure at ambient temperature greater than boiling point under the stable organic compound of 133.32Pa or the normal pressure.
15. method as claimed in claim 14, wherein said organic compound is selected from one or more in toluene, benzene, styrene, dimethylbenzene, biphenyl, naphthalene, anthracene, phenanthrene, ethanol, acetonitrile, ethyl acetate, propyl alcohol, acetone, propylene glycol, the butanone.
16. LiMPO by each described method acquisition in the above claim
4/ C composite material, wherein M is metal or its combination that is selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn, described LiMPO
4The average grain diameter of/C composite material is in 0.02 μ m to 1.0 mu m range, and carbon-coating thickness is in 0.001 to 0.1 mu m range.
17. contain the described LiMPO of claim 16
4The electrode of/C composite material.
18. contain the described LiMPO of claim 16
4The battery of/C composite material.
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| CN104953094A (en) * | 2015-06-24 | 2015-09-30 | 合肥国轩高科动力能源股份公司 | Method for preparing lithium iron phosphate having high tap density |
| CN108063248A (en) * | 2017-10-29 | 2018-05-22 | 佛山市德方纳米科技有限公司 | Lithium iron phosphate positive material and preparation method thereof and lithium ion battery |
| CN109244434A (en) * | 2018-11-18 | 2019-01-18 | 河南科技学院 | A kind of GaP@C composite and preparation method thereof and the application in cathode of lithium battery |
| CN110914194A (en) * | 2017-07-19 | 2020-03-24 | 纳诺万材料公司 | Improved synthesis of olivine-type lithium metal phosphate positive electrode materials |
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| CN101237039A (en) * | 2008-01-08 | 2008-08-06 | 上海大学 | Method for synthesizing LiFePO4/C material based on chemical gas phase sediment auxiliary solid phase method |
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