CN102468481B - Method for preparing polyanionic cathode material used for lithium ion battery - Google Patents
Method for preparing polyanionic cathode material used for lithium ion battery Download PDFInfo
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- CN102468481B CN102468481B CN201010540801.9A CN201010540801A CN102468481B CN 102468481 B CN102468481 B CN 102468481B CN 201010540801 A CN201010540801 A CN 201010540801A CN 102468481 B CN102468481 B CN 102468481B
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Abstract
The invention discloses a method for preparing a polyanionic cathode material used for a lithium ion battery by sol-gel. The method comprises the following steps: mixing lithium salt, transition metal salt, a polyanionic predecessor and carbon source according to certain stoichiometric ratio to prepare a sol, then adding an organic epoxide under certain condition to prepare a gel, drying and calcining to prepare the polyanionic cathode material. The preparation method is simple and easy to operate, the reactant enables uniform mixing, and the gel is easy to form; compared with a solid phase synthesis method, the calcining temperature and calcining time are reduced, compared with other sol-gel method, the method of the invention has the advantages of fast gel forming and short synthesis time, and is suitable for industrial production. The polyanionic cathode material has the advantages of small particle size, uniform distribution, large specific surface and the like; especially has the good charge and discharge performance, multiplying power performance and low temperature performance.
Description
Technical field
The present invention relates to polyanionic cathode material used for lithium ion battery, say more specifically a kind of preparation method of anode material for lithium-ion batteries.
Background technology
In existing secondary cell, lithium ion battery has the highest volume and mass energy density, is current state-of-the-art secondary cell.In addition, lithium ion battery also have have extended cycle life, memory-less effect and the advantage such as self-discharge rate is low.At present, be widely used in various portable type electronic products, and become the first-selected electrical source of power of electric motor car and hybrid electric vehicle.
Polyanion type positive electrode has high cyclical stability and thermal stability, and abundant raw material is easy to get, and environmental friendliness is expected to become anode material for lithium-ion batteries of new generation.
Polyanion type positive electrode is because polyanion unit (XO
4)
y-(X=P, Si, As, Ge etc.) are spaced apart by metal ion, cause the electronic conductivity of material lower.Generally, people are coated by electronics good conductor surface, body phase metal ion mixing or prepare nano level active material particle, increase the method such as electrically contact between active material and conductive agent and collector, improve the conductivity of material.
1997, the first passage solid phase methods such as Goodenough synthesized LiFePO
4and LiFe
1-xmn
xpO
4(Phospho-olivines as Positive-Electrode Materials for Rechargeable Lithium Batteries, Journal of Electrochemical Society, 1997,144 (4): 1188-1194); 1998, Shackle adopted first liquid phase synthesizing method and hydrothermal synthesis method to synthesize Li in patent US5721070
2mnSiO
4, employing silicate has been proposed first as anode material for lithium-ion batteries; 2000, Armand etc. proposed with Li first in patent US6085015
2feSiO
4positive electrode as lithium ion battery.
At present, the method for synthesis nano polyanionic lithium ion battery anode material mainly contains high temperature solid-state method, microwave method, solvent heat synthetic method, sol-gel process, coprecipitation, liquid phase reduction and curtain coating Xiang Fa etc.D.Y. Wang etc. is with FeC
2o
42H
2o, NH
4h
2pO
4with LiF be raw material, after ball milling mixes, at 400 ℃ and 600 ℃, calcining certain hours successively, to have obtained particle diameter be the pure phase LiFePO of 300 ~ 600 nm
4(Cracking causing cyclic instability of LiFePO
4cathode material, Journal of Power Sources, 2005,140:125-128); B.W. Kang etc. is with Li
2cO
3, FeC
2o
42H
2o and NH
4h
2pO
4for raw material, adopt high temperature solid phase synthesis, make the LiFePO of particle diameter approximately 50 nm
4, material list reveal excellent chemical property (Battery materials for ultrafast charging and discharging, Nature, 2009,458:190-193); H.L. Zou etc. is with FePO
44H
2o and Li
2cO
3or LiOHH
2o is raw material, and adopting microwave method to synthesize particle diameter is the LiFePO of 50 ~ 100 nm
4(Intermittent microwave heating synthesized high performance spherical LiFePO
4/ C for Li-ion batteries, Materials Research Bulletin, 2010,45:149-152); Z.D. Peng etc. utilizes microwave method to synthesize Li
2feSiO
4(Microwave synthesis of Li
2feSiO
4cathode materials for lithium-ion batteries, Chinese Chemical Letters, 2009,20:1000-1004); J.F. Ni etc. be take organic acid as template, adopts hydro thermal method to synthesize the LiFePO of particle diameter 50 ~ 100 nm
4particle (Hydrothermal preparation of LiFePO
4nanocrystals mediated by organic acid, J. of Power Sources, 2010,195:2877-2882); Z.L. Gong etc. is with LiAc2H
2o, Fe (Ac)
2, tetraethoxysilane (TEOS) is raw material, take HAc as catalyst, adopts hydro thermal method to synthesize the Li of particle diameter 40 ~ 80 nm
2feSiO
4particle (Nanostructured Li
2feSiO
4electrode Material Synthesized through Hydrothermal-Assisted Sol-Gel Process, Electrochemical and Solid-State Letters, 2008,11 (5): A60-A63); S.F. the employing hydrothermal synthesis method such as Yang has synthesized LiFePO
4(Reactivity, stability and electrochemical behavior of lithium iron phosphates, Electrochemical communication, 2002,4:239-244); C. Deng etc. is by LiAc, Mn (Ac)
2, tetraethoxysilane (TEOS) and citric acid be at 75 ℃ of evaporation waters and ethanol, first obtains Li
2mnSiO
4gel has obtained nano level Li after high-temperature calcination
2mnSiO
4(Characterization of Li
2mnSiO
4and Li
2feSiO
4cathode materials synthesized via a citric acid assisted sol – gel method, Materials Chemistry and Physics, 2010,120:14-17); Z.H. Xu etc. is with H
3pO
4, Fe (NO
3)
3, CH
3cOOLi, citric acid and polyethylene glycol are raw material, make nano level LiFePO
4material (A PEG assisted sol – gel synthesis of LiFePO
4as cathodic material for lithium ion cells, Materials Research Bulletin, 2007,42:883-891); D.W. Choi etc. is with CH
3cOOLi2H
2o, FeCl
24H
2o and P
2o
5for raw material, laurate is that surfactant and carbon source have been synthesized the LiFePO that particle diameter is less than 65nm
4(Surfactant based sol – gel approach to nanostructured LiFePO
4for high rate Li-ion batteries, J. of Power Sources, 2007,163:1064-1069); K.F. Hsu etc. adopts citric acid, and transpiring moisture has obtained LiFePO at a certain temperature
4gel (Synthesis and characterization of nano-sized LiFePO
4cathode materials prepared by a citric acid-based sol – gel route, Journal of materials Chemistry, 2004,14:2690-2695); Dominko etc. utilize modification sol gel method to synthesize Li
2mnSiO
4(Li
2mSiO
4(M=Fe and/or Mn) cathode materials, Journal of Power Sources, 2008,184:462-468); K.S. Park etc. is with (NH
4)
2fe (SO
4)
26H
2o, H
3pO
4with LiOH be raw material, with ammoniacal liquor, regulate pH to make precipitation, after microwave heating, obtain nanoscale LiFePO
4(Synthesis of LiFePO
4by co-precipitation and microwave heating, Electrochemistry Communications, 2003,5:839-842); B.F. first Wang etc. makes FePO
4, after in liquid phase, with ascorbic acid, reduce FePO
4, obtain particle diameter at the LiFePO of 150 nm
4(Ultrafine LiFePO
4cathode materials synthesized by chemical reduction and lithiation method in alcohol solution, Solid State Ionics, 2007,178:843-847); The people such as Zhang Zhongtai adopt liquid phase reduction to synthesize LiFePO in patent CN1469499A
4; Y.H. Huang etc. is with FePO
4, LiOHH
2o and soluble starch are raw material, add a small amount of deionized water and grind evenly, obtain curtain coating phase slurry, obtain the nanometer LiFePO of 100 ~ 200 nm after high-temperature calcination
4(Synthesis of LiFePO
4/ carbon composite from nano-FePO
4by a novel stearic acid assisted rheological phase method, Electrochimica Acta, 2009,55:311-315).
In sum, the preparation LiFePO of existing document or patent report
4in method, adopt polyethylene glycol (PEG), citric acid or the gelling agents such as mixture of the two or the method by evaporating solvent to obtain gel, will after gel calcining, obtain polyanionic cathode material used for lithium ion battery.
Organic epoxide, if oxolane, oxirane, expoxy propane, epoxychloropropane, pyridine etc. are a kind of gel promoter, is applied to preparing aeroge.U.S. Lorenz-Li Wo More National Laboratory has reported and has utilized expoxy propane to prepare Ni-based, iron-based and chromium base porous aerogel as gel promoter; The people such as the Zhou Bin of Shanghai Tongji University have reported and have utilized polyacrylic acid for dispersant, and expoxy propane is that gel promoter is prepared multiple transition metal aeroge; J. W. Long etc. has reported and has utilized epoxychloropropane to prepare Mn/Fe composite transition metal oxide silica aerogel for gel promoter; Wang Xitao, clock are genial etc. has reported the catalyst ferric phosphate for the preparation of catalysis ethane partial oxidation with expoxy propane.
Have not yet to see about utilizing organic epoxide to prepare the report of the sol-gel process of polyanionic cathode material used for lithium ion battery.
Summary of the invention
The object of the present invention is to provide a kind of method of utilizing sol-gel process to prepare polyanionic cathode material used for lithium ion battery.
For achieving the above object, the technical solution used in the present invention is:
A kind of preparation method of polyanionic cathode material used for lithium ion battery:
1) lithium salts, transition metal salt, polyanion predecessor, carbon source dissolved or disperseed in solvent, making colloidal sol;
2) under stirring condition, in above-mentioned colloidal sol, drip or add organic epoxide in batches, when changing gel into, colloidal sol stops;
3) by step 2) in the gel that makes aging after, dry, obtain xerogel;
4) by the xerogel making in step 3) in reducing atmosphere, in 400 ~ 1000 ℃ calcining 0.5 ~ 24 h, make the nanoscale polyanion type positive electrode with good crystallinity.
Concrete steps are:
(1) lithium salts A and transition metal salt B are added in solvent C, the molar concentration that is made into A and B is respectively the solution D of 0.01 ~ 4 M, and the molar concentration of A and B is preferably 0.5 ~ 4 M, and optimum is 1 ~ 3.5 M; Polyanion predecessor E is added in solvent F, be made into the solution G of molar concentration 0.01 ~ 4 M, wherein the molar concentration of E is preferably 0.5 ~ 3 M, and optimum is 1 ~ 3 M; Wherein, the mol ratio of lithium ion and transition metal ions is (0.9 ~ 2): (0.9 ~ 2), is preferably 1 ~ 2.1;
(2) press transition metal ions in transition metal salt B: in polyanion predecessor E, the mol ratio of polyanion is (0.9 ~ 1.5): (0.9 ~ 1.5), preferred 1:1 ~ 1.5, solution G is dropwise added in solution D, and add carbon source H simultaneously, obtain colloidal sol I, the molar concentration of the carbon source H adding in colloidal sol I is 0.01 ~ 4 M;
(3) reaction temperature is constant in 10 ~ 50 ℃, be preferably 15 ~ 30 ℃, with the speed of 40 ~ 1000 revs/min, stir, to making in step (2), in colloidal sol I, drip or add organic epoxide in batches, when becoming gel J, colloidal sol stops; Wherein, add in the process of organic epoxide, the pH value of controlling colloidal sol over time rate (
pH/min) remain on 0.01 ~ 4, be preferably 0.01 ~ 3, obtain the finely dispersed jelly shape of each component gel;
(4) by the gel J making in step (3) after 20 ~ 60 ℃ of aging 1 ~ 240 h, in 30 ~ 200 ℃ of dry 1 ~ 24 h, obtain xerogel K; Wherein, aging temperature is preferably 20 ~ 50 ℃, and ageing time is preferably 24 ~ 48 h; Baking temperature is preferably 60 ~ 120 ℃, is preferably 10 ~ 24 h drying time;
(5) by the xerogel K making in step (4) in reducing atmosphere, in 400 ~ 1000 ℃ calcining 0.5 ~ 24 h, make the nanoscale polyanion type positive electrode with good crystallinity; Wherein, calcining heat is preferably 600 ~ 900 ℃, and calcination time is preferably 2 ~ 20 h;
Described organic epoxide is one or more in oxolane, oxirane, expoxy propane, epoxychloropropane, pyridine.
Solvent for use C or solvent F are respectively one or more in deionized water, methyl alcohol, absolute ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, propionitrile, formaldehyde, dimethyl formamide, ethylene glycol, propylene glycol, dimethyl sulfoxide (DMSO).
Described lithium salts A is one or more in lithium sulfate, sulfuric acid monohydrate lithium, lithium acetate, lithium nitrate, nitrate trihydrate lithium, lithium dihydrogen phosphate, lithium chloride, a water lithium chloride, lithium oxalate; Preferably lithium nitrate, nitrate trihydrate lithium, lithium dihydrogen phosphate, lithium chloride, a water lithium chloride, lithium acetate, in one or more.
Described transition metal salt B is one or more in the chloride, bromide, nitrate, sulfate, dibasic alkaliine, dihydric phosphate, acetate of I B, II B, III B, IV B, V B, VI B, VII B or VIII B transition metal ions; One or more in the chloride of preferred Fe, Mn, Co, Ni, V, bromide, nitrate, sulfate, acetate.
Described polyanion precursor E is phosphoric acid, sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, lithium dihydrogen phosphate, three water ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, tetramethylsilane, tetraethyl silane, tetrapropyl silane, tetrabutyl silane, sodium metasilicate, silicic acid, silicon tetrachloride, siloxanes containing one or more in the compound of polyanion; One or more in preferably phosphoric acid, three water ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, tetramethylsilane, tetraethyl silane, tetrapropyl silane, tetrabutyl silane.
Described carbon source H is one or more in glucose, citric acid, sucrose, acetylene black, XC-72, BP-2000, super P, the molecular weight polyethylene glycol that is 200 ~ 20000, starch, cyclodextrin, polyacrylic acid; One or more in preferred glucose, citric acid, sucrose, acetylene black, XC-72, BP-2000, super P.
Reducing atmosphere used one or both gaseous mixtures that form in hydrogen and nitrogen or argon gas, wherein the volume content of hydrogen is 5 ~ 10 %; The gaseous mixture of preferred hydrogen and argon gas, the volume content of hydrogen is 5 ~ 10 %.
the beneficial effect that the present invention has is:
Utilize slaine, adopting sol-gel process to prepare in the reaction of lithium ion battery polyanion type positive electrode, by the size decision transition metal salt of reaction equilibrium constant, or hydrolysis is occurring, generating insoluble hydroxide of metal; Or react with polyanion, generate insoluble metal polyanionic salt.When product particle concentration is lower and adsorption has compared with multi-charge, form colloidal sol; Otherwise, generate precipitation.In colloidal sol, micelle concentration raises, and the electric charge on micelle surface is neutralized gradually, and gelation energy barrier reduces gradually, micelle particle generation polycondensation reaction, and form gradually gel.
The present invention is utilizing slaine and is adopting sol-gel process to prepare in the reaction of lithium ion battery polyanion type positive electrode, and use organic epoxide (as expoxy propane) etc. has been accelerated the formation of gel, and prepared gel is transparent jelly shape gel.The concrete effect of organic epoxide in this reaction system:
(1) under proton catalysis, there is opening (take expoxy propane as example) in organic epoxide:
Reaction 1
Reaction 2
The opening of organic epoxide under proton catalysis is as shown in reaction equation 1 and 2.Reaction 1 represents organic epoxide and nucleopilic reagent A
-reaction consume H
+the pH value of system is raise, and promoted reacting of the hydrolysis of transition metal ions or transition metal ions and polyanion, all generate more micelle.Reaction 2 represents that the opening of organic epoxide and water has consumed the water in system, but does not change the pH value of system.Above-mentioned two reactions all generate alcohol.
(2) in the involved in the present invention sol system that contains many kinds of metal ions predecessor, the opening of organic epoxide consumes proton, reduced gradually positive charge (proton) quantity on micelle surface, the lithium ion being conducive in solution is adsorbed in micelle surface, after forming gel, can obtain height homogeneous and the stable polynary predecessor of polyanion type positive electrode.
(3) in the involved in the present invention sol-gel process for preparing that utilizes slaine, use appropriate organic epoxide, the proton in organic epoxide and system and the opening of nucleopilic reagent, promote the rising of micelle concentration; In organic epoxide and system, the opening of water has consumed water, has further improved the concentration of micelle in system; Above-mentioned two kinds of effects have promoted the conversion of colloidal sol to gel jointly, have accelerated the gelation of sol system.And, adopt method of the present invention to make gel at normal temperature, avoided the process of the evaporation and concentration plastic used in other sol-gel process.
(4) in the sol system of the involved in the present invention many kinds of metal ions predecessor that contains higher concentration, by controlling the rate of change of sol system pH value, the speed of organic epoxide is added in regulation and control, regulate and control the speed of organic epoxide opening, realized the stable of gel and formed fast.Simultaneously, because the opening of organic epoxide has also reduced the free ion number in sol system, therefore, adopt organic epoxide as gel promoter, the flocculation that can effectively avoid in sol system the rapid polymerization due to micelle to cause.
Simultaneously, the present invention is also optimized the preparation technology of the polynary collosol-gelatum system of polyanion type positive electrode, comprise: by optimizing the concentration of each component in same system, improved the concentration of the predecessor of synthesized gel rubber, made highly homogeneous jelly shape gel; By optimizing mole when concentration of carbonaceous material of lithium ion and transition metal ions, make the positive electrode that chemical property is good; By optimizing the follow-up calcine technology parameter of gel aging temperature, material etc., finally make the anode material for lithium-ion batteries that chemical property is good.Electro-chemical test shows, the polyanionic lithium ion battery anode material that uses the inventive method to prepare has excellent reversible charge-discharge performance, cyclical stability, high rate performance and cryogenic property.
In sum, major advantage of the present invention is, preparation of sol-gel process is simple to operation and can normal temperature preparation, and predecessor concentration is high, and calcining heat is low, is conducive to the industrialization of the method.
Accompanying drawing explanation
Fig. 1 is LiFePO
4the X-ray diffractogram of/C;
Fig. 2 is LiFePO
4the SEM figure of/C;
Fig. 3 is the LiFePO that embodiment 1 obtains
4charging and discharging curve;
Fig. 4 is the LiFePO that embodiment 1 obtains
4multiplying power discharging curve;
Fig. 5 is the LiFePO that embodiment 2 obtains
4charging and discharging curve;
Fig. 6 is the LiFePO that embodiment 3 obtains
4cycle performance curve;
Fig. 7 is the LiFePO that embodiment 4 obtains
4charging and discharging curve;
Fig. 8 is the Li that embodiment 6 obtains
2mnSiO
4charging and discharging curve;
Fig. 9 is the Li that embodiment 11 obtains
3v
2(PO
4)
3the cycle performance curve of/C;
Figure 10 is the LiFePO that comparative example 1 obtains
4charging and discharging curve.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited to following examples.
embodiment 1
By 0.0325 g FeCl
3, 0.0230 g LiNO
3be dissolved in 10 mL deionized waters, stir about 4 h then dropwise drip the NH that concentration is 0.33 M in above-mentioned solution
4h
2pO
4the aqueous solution 10 mL, obtain colloidal sol.In this colloidal sol, add 0.0396 g glucose.Under the condition of 2 ℃ of constant temperature, in this colloidal sol, dropwise drip 20 mL expoxy propane, the pH value of controlling colloidal sol over time rate (
pH/min) be 0.5 ~ 0.8, obtain the gel of the homodisperse jelly shape of each predecessor component.By aging one day of this gel, then 60 ℃ of dry 24 h in air successively, obtained LiFePO
4predecessor.Finally, at Ar/H
2(H in gaseous mixture
2volume fraction be 10 %), 600 ℃ of calcining predecessor 10 h obtain product LiFePO
4/ C, its XRD spectra is shown in Fig. 1.
By the LiFePO of preparation
4/ C, as anode material for lithium-ion batteries, is mixed to get slurry with acetylene black, PVDF according to the ratio of mass ratio 75:15:10.Slurry is evenly coated on aluminium foil and obtains work electrode, take lithium sheet as to electrode, Celgard 2340 polypropylene screens are barrier film, 1 M LiPF
6/ EC+DMC (EC:DMC=1:1) is electrolyte, in being full of the glove box of argon gas, is assembled into button cell.
Above-mentioned battery is discharged and recharged and on instrument, carries out charge-discharge test at Neware.Charging/discharging voltage scope 2.0 ~ 4.2 V.Charge-discharge test shows, material at 0.2 C specific discharge capacity up to 150 mAhg
-1, the specific discharge capacity of 1 C still approaches 140 mAhg
-1, show higher charging and discharging capacity and good high rate performance (seeing Fig. 3 and 4).
embodiment 2
By 4.064 g Fe
2(SO
4)
39H
2o, 5.516 g LiNO
3be dissolved in 10 mL deionized waters, stir about 4 h then dropwise drip the NH that concentration is 0.08 mol in above-mentioned solution
4h
2pO
4the aqueous solution 10 mL, obtain colloidal sol.Meanwhile, in this colloidal sol, add 15.8536 g acetylene blacks., under the condition of 50 ℃ of constant temperature, in this colloidal sol, dropwise drip 2 mL expoxy propane, the pH value of controlling colloidal sol over time rate (
pH/min) be 2 ~ 2.4, obtain the gel of the homodisperse jelly shape of each predecessor component.By aging 1 h of this gel, then, at 200 ℃ of dry 1 h, obtain LiFePO
4head product.Finally, at Ar/H
2(H in gaseous mixture
2volume fraction be 10 %), 800 ℃ calcining LiFePO
4head product 0.5 h obtains end-product LiFePO
4/ C.
By the LiFePO of preparation
4/ C, as anode material for lithium-ion batteries, is mixed to get slurry with acetylene black, PVDF according to the ratio of mass ratio 75:15:10.Slurry is evenly coated on aluminium foil and obtains work electrode, take lithium sheet as to electrode, Celgard 2340 polypropylene screens are barrier film, 1 M LiPF
6/ EC+DMC (EC:DMC=1:1) is electrolyte, in being full of the glove box of argon gas, is assembled into button cell.
Above-mentioned battery is discharged and recharged and on instrument, carries out charge-discharge test at Neware.Charging/discharging voltage scope 2.0 ~ 4.2 V.This product has good chemical property, and as shown in Figure 5, with 0.2 C constant current charge-discharge, the specific discharge capacity of material is up to 140 mAhg for the charging and discharging curve of material
-1.The pattern of material is shown in Fig. 2.
embodiment 3
By 20.0 g Fe
2(SO
4)
39H
2o, 2.758 g LiNO
3be dissolved in 10 mL deionized waters, stir about 4 h then dropwise drip the NH that concentration is 4 M in above-mentioned solution
4h
2pO
4the aqueous solution 10 mL, obtain colloidal sol.Meanwhile, in this colloidal sol, add 6.8458 g sucrose, under the condition of 2 ℃ of constant temperature, in this colloidal sol, dropwise drip 20 mL epoxychloropropane, the pH value of controlling colloidal sol over time rate (
pH/min) be 0.03 ~ 0.1, obtain the gel of the homodisperse jelly shape of each predecessor component.By aging one day of this gel, then, at 30 ℃ of dry 24 h, obtain LiFePO
4predecessor.Finally, at Ar/H
2(H in gaseous mixture
2volume fraction be 10 %), 600 ℃ of calcining predecessor 10 h obtain product LiFePO
4/ C.
By the LiFePO of preparation
4/ C, as anode material for lithium-ion batteries, is mixed to get slurry with acetylene black, PVDF according to the ratio of mass ratio 75:15:10.Slurry is evenly coated on aluminium foil and obtains work electrode, take lithium sheet as to electrode, Celgard 2340 polypropylene screens are barrier film, 1 M LiPF
6/ EC+DMC (EC:DMC=1:1) is electrolyte, in being full of the glove box of argon gas, is assembled into button cell.
Above-mentioned battery is discharged and recharged and on instrument, carries out charge-discharge test at Neware.Charging/discharging voltage scope 2.0 ~ 4.2 V.1 C constant current charge-discharge, after 200 circulations, product LiFePO
4the capability retention of/C is shown in Fig. 6 up to 94 %().
embodiment 4
By 1.616 g Fe (NO
3)
39H
2o, 0.3310 g LiCl are dissolved in 10 mL deionized waters,, then in above-mentioned solution, dropwise drip the H that concentration is 0.4 M
3pO
4the aqueous solution 10 mL, obtain colloidal sol.Meanwhile, in this colloidal sol, add 0.0793 g glucose, under the condition of 50 ℃ of constant temperature, in this colloidal sol, dropwise drip 4 mL expoxy propane, the pH value of controlling colloidal sol over time rate (
pH/min) be 2.5 ~ 3.1, obtain the gel of the homodisperse jelly shape of each predecessor component.By aging one day of this gel, then, at 150 ℃ of dry 10 h, obtain LiFePO
4predecessor.Finally, at Ar/H
2(H in gaseous mixture
2volume fraction be 10 %), 400 ℃ of calcining predecessor 24 h obtain product LiFePO
4/ C.
By the LiFePO of preparation
4/ C, as anode material for lithium-ion batteries, is mixed to get slurry with acetylene black, PVDF according to the ratio of mass ratio 75:15:10.Slurry is evenly coated on aluminium foil and obtains work electrode, take lithium sheet as to electrode, Celgard 2340 polypropylene screens are barrier film, 1 M LiPF
6/ EC+DMC (EC:DMC=1:1) is electrolyte, in being full of the glove box of argon gas, is assembled into button cell.
Above-mentioned battery is discharged and recharged and on instrument, carries out charge-discharge test at Neware.Charging/discharging voltage scope 2.0 ~ 4.2 V.Product has good chemical property, 0.2 C constant current charge-discharge, and charge ratio capacity is up to 150 mAhg
-1(as shown in Figure 7).
embodiment 5
By 4.52 g LiNO
3be dissolved in the Mn (NO of 15 mL mass fraction 50 %
3)
2the aqueous solution, stir about 4 h then dropwise drip the NH that concentration is 0.327 M in above-mentioned solution
4h
2pO
4the aqueous solution 20 mL, obtain colloidal sol.In this colloidal sol, add 0.0396 g sucrose.In room temperature, in this colloidal sol, dropwise drip 20 mL oxirane, the pH value of controlling colloidal sol over time rate (
pH/min) be 3.0 ~ 4.0, obtain the gel of the homodisperse jelly shape of each predecessor component.By aging 240 h of this gel, then 60 ℃ of dry 24 h in air successively, obtain LiMnPO
4predecessor.Finally, at Ar/H
2(H in gaseous mixture
2volume fraction be 5%), 600 ℃ of calcining predecessor 10 h obtain product LiMnPO
4/ C.
By the LiMnPO of preparation
4/ C, as anode material for lithium-ion batteries, is mixed to get slurry with acetylene black, PVDF according to the ratio of mass ratio 75:15:10.Slurry is evenly coated on aluminium foil and obtains work electrode, take lithium sheet as to electrode, Celgard 2340 polypropylene screens are barrier film, 1 M LiPF
6/ EC+DMC (EC:DMC=1:1) is electrolyte, in being full of the glove box of argon gas, is assembled into button cell.
Above-mentioned battery is discharged and recharged and on instrument, carries out charge-discharge test at Neware.Charging/discharging voltage scope 2.0 ~ 4.2 V.Product LiMnPO
4/ C can reversiblely discharge and recharge, 0.2 C constant current charge-discharge, and charging and discharging capacity is 150 mAhg
-1.
embodiment 6
To the Mn (NO that pipettes 13.72 mL mass fraction 50 % in 150 mL beakers
3)
2the aqueous solution, then adds 9.28 mL deionized waters and 8.27 g LiNO successively
3, 10.2687 g sucrose, treat LiNO
3, sucrose dropwise adds ethanolic solution 5 mL of the tetraethoxysilane of 0.06moL after dissolving completely.Under room temperature, dropwise add 30 mL expoxy propane, the pH value of controlling colloidal sol over time rate (
pH/min) be 2.1 ~ 2.6, obtain the homodisperse jelly shape of each predecessor component gel.This gel, after aging one day, in 85 ℃ of dry 10 h, is obtained to LiMnSiO
4predecessor.Finally, at Ar/H
2(H in gaseous mixture
2volume fraction be 10 %), 680 ℃ calcining 10 h obtain end product Li
2mnSiO
4/ C.
By the LiMnSiO of preparation
4/ C, as anode material for lithium-ion batteries, is mixed to get slurry with acetylene black, PVDF according to the ratio of mass ratio 75:15:10.Slurry is evenly coated on aluminium foil and obtains work electrode, take lithium sheet as to electrode, Celgard 2340 polypropylene screens are barrier film, 1 M LiPF
6/ EC+DMC (EC:DMC=1:1) is electrolyte, in being full of the glove box of argon gas, is assembled into button cell.
Above-mentioned battery is discharged and recharged and on instrument, carries out charge-discharge test at Neware.Charging/discharging voltage scope 1.5 ~ 4.8 V, the charge-discharge performance of test battery.Product Li
2mnSiO
4/ C has good chemical property, 20 mAg
-1constant current charge-discharge, initial charge specific capacity reaches 301 mAh/g(as shown in Figure 8), approach theoretical specific capacity.
embodiment 7
By 8.1087 g FeCl
36H
2o, 4.137 g LiNO
3be dissolved in 15 mL deionized waters, then in above-mentioned solution, dropwise drip ethanolic solution 5 mL that concentration is the silicic acid orthocarbonate of 4 M, obtain colloidal sol.Meanwhile, in this colloidal sol, add 5.1063 g sucrose.At room temperature, in this colloidal sol, dropwise drip 25 mL expoxy propane, the pH value of controlling colloidal sol over time rate (
pH/min) be 1.8 ~ 2.2, obtain the gel of the homodisperse jelly shape of each predecessor component.By aging one day of this gel, then, at 120 ℃ of dry 10 h, obtain Li
2feSiO
4predecessor.Finally, at Ar/H
2(H in gaseous mixture
2volume fraction be 10 %), 680 ℃ calcining 10 h obtain product Li
2feSiO
4/ C.
By the Li of preparation
2feSiO
4/ C, as anode material for lithium-ion batteries, is mixed to get slurry with acetylene black, PVDF according to the ratio of mass ratio 75:15:10.Slurry is evenly coated on aluminium foil and obtains work electrode, take lithium sheet as to electrode, Celgard 2340 polypropylene screens are barrier film, 1 M LiPF
6/ EC+DMC (EC:DMC=1:1) is electrolyte, in being full of the glove box of argon gas, is assembled into button cell.
Above-mentioned battery is discharged and recharged and on instrument, carries out charge-discharge test at Neware.Charging/discharging voltage scope 1.5 ~ 4.5 V.With 20 mAg
-1constant current charge-discharge, the Li making in 1.5 ~ 4.5 V intervals
2feSiO
4the charging and discharging capacity of/C is 155 mAhg
-1, approach the corresponding Li in this interval
+reversible embedding/de-theoretical specific capacity.
embodiment 8
To the Mn (NO that pipettes 6.86 mL mass fraction 50 % in 150 mL beakers
3)
2the aqueous solution, then adds 0.03 mol FeCl successively
36H
2o, 13.14 mL deionized waters and 8.27 g LiNO
3, 10.2687g sucrose, stir 2 h and treat FeCl
3.6H
2o, LiNO
3ethanolic solution 5 mL that dropwise add the tetraethoxysilane that contains 0.06 mol after dissolving completely with sucrose.Under room temperature, dropwise add 30 mL expoxy propane, the pH value of controlling colloidal sol over time rate (
pH/min) be 1.5 ~ 1.9, obtain the homodisperse jelly shape of each predecessor component gel.This gel, after aging one day, is obtained to LiMn in 85 ℃ of dry 10 h
0.5fe
0.5siO
4predecessor.Finally, at Ar/H
2(H in gaseous mixture
2volume fraction be 10 %), 680 ℃ calcining 10 h obtain end-product Li
2mn
0.5fe
0.5siO
4/ C.
By the Li of preparation
2mn
0.5fe
0.5siO
4/ C, as anode material for lithium-ion batteries, is mixed to get slurry with acetylene black, PVDF according to the ratio of mass ratio 75:15:10.Slurry is evenly coated on aluminium foil and obtains work electrode, take lithium sheet as to electrode, Celgard 2340 polypropylene screens are barrier film, 1 M LiPF
6/ EC+DMC (EC:DMC=1:1) is electrolyte, in being full of the glove box of argon gas, is assembled into button cell.
Above-mentioned battery is discharged and recharged and on instrument, carries out charge-discharge test at Neware.Charging/discharging voltage scope 1.5 ~ 4.8 V.With 20 mAg
-1constant current charge-discharge, the Li making
2mn
0.5fe
0.5siO
4/ C capability retention after 50 circulations reaches 80 %.
embodiment 9
By 0.0475 g CoCl
26H
2o, 0.0230 g LiNO
3be dissolved in 10 mL deionized waters, stir about 4 h then dropwise drip the NH that concentration is 0.33 M in above-mentioned solution
4h
2pO
4the aqueous solution 10 mL, obtain colloidal sol.In this colloidal sol, add 0.013 g glucose.Under the condition of 2 ℃ of constant temperature, in this colloidal sol, dropwise drip 20 mL expoxy propane, the pH value of controlling colloidal sol over time rate (
pH/min) be 1.1 ~ 1.5, obtain the gel of the homodisperse jelly shape of each presoma component.By aging one day of this gel, then 60 ℃ of dry 24 h in air, obtained LiCoPO
4presoma.Finally, at Ar/H
2(H in gaseous mixture
2volume fraction be 10%), 600 ℃ calcining 10 h obtain product LiCoPO
4/ C.
By the LiCoPO of preparation
4/ C positive electrode and acetylene black, PVDF are mixed to get slurry according to the ratio of mass ratio 75:15:10.Slurry is evenly coated on aluminium foil and obtains work electrode, take lithium sheet as to electrode, Celgard 2340 polypropylene screens are barrier film, 1 M LiPF
6/ EC+DMC (EC:DMC=1:1) is electrolyte, in being full of the glove box of argon gas, is assembled into button cell.
Above-mentioned battery is discharged and recharged and on instrument, carries out charge-discharge test, charging/discharging voltage scope 3.0 ~ 5.0V at Neware.Test result demonstration, material discharges and recharges with 0.1 C, and specific discharge capacity reaches 100 mAhg
-1, show higher charging and discharging capacity.
By 19.46 g FeCl
36H
2o, 2.3265 g Ni (NO
3)
26H
2o, 5.516 g LiNO
3be dissolved in 10 mL deionized waters, stir about 4 h then dropwise drip and contain 0.08 mol NH in above-mentioned solution
4h
2pO
4the aqueous solution 10 mL, obtain colloidal sol.Meanwhile, in this colloidal sol, add 15.8536 g acetylene blacks, 50 ℃ of steady temperatures dropwise drip 2 mL expoxy propane in this colloidal sol, the pH value of controlling colloidal sol over time rate (
pH/min) be 0.7 ~ 1.1, obtain the homodisperse jelly shape of each presoma component gel.By aging 1 h of this gel, then, at 200 ℃ of dry 1 h, obtain LiFe
0.9ni
0.1pO
4head product.Finally, at Ar/H
2(H in gaseous mixture
2volume fraction be 10 %), 800 ℃ calcining 0.5 h obtain end-product LiFe
0.9ni
0.1pO
4/ C.
By the LiFe of preparation
0.9ni
0.1pO
4/ C positive electrode and acetylene black, PVDF are mixed to get slurry according to the ratio of mass ratio 75:15:10.Slurry is evenly coated on aluminium foil and obtains work electrode, take lithium sheet as to electrode, Celgard 2340 polypropylene screens are barrier film, 1 M LiPF
6/ EC+DMC (EC:DMC=1:1) is electrolyte, in being full of the glove box of argon gas, is assembled into button cell.
Above-mentioned battery is discharged and recharged and on instrument, carries out charge-discharge test at Neware.Test result demonstration, this product has good chemical property, and with 0.1 C constant current charge-discharge, specific discharge capacity reaches 160 mAhg
-1.
embodiment 11
By 6.52 g VOSO
4xH
2o, 4.1352 g LiNO
3be dissolved in 10 mL deionized waters, stir about 4 h then dropwise drip the NH that concentration is 6 M in above-mentioned solution
4h
2pO
4the aqueous solution 10 mL, obtain colloidal sol.Then, in this colloidal sol, add 6.8458 g sucrose, under the condition of 2 ℃ of constant temperature, in this colloidal sol, dropwise drip 20 mL epoxychloropropane, the pH value of controlling colloidal sol over time rate (
pH/min) be 0.1 ~ 0.5, obtain the homodisperse jelly shape of each presoma component gel.By aging one day of this gel, then, at 30 ℃ of dry 24 h, obtain Li
3v
2(PO
4)
3presoma.Finally, at Ar/H
2(H in gaseous mixture
2volume fraction be 10%), 600 ℃ calcining 10 h obtain product Li
3v
2(PO
4)
3/ C.
By the Li of preparation
3v
2(PO
4)
3/ C positive electrode and acetylene black, PVDF are mixed to get slurry according to the ratio of mass ratio 75:15:10.Slurry is evenly coated on aluminium foil and obtains work electrode, take lithium sheet as to electrode, Celgard 2340 polypropylene screens are barrier film, 1 M LiPF
6/ EC+DMC (EC:DMC=1:1) is electrolyte, in being full of the glove box of argon gas, is assembled into button cell.
Above-mentioned battery is discharged and recharged on instrument and carries out charge-discharge test at Neware, and voltage range is 3.0 ~ 4.3 V.Test result as shown in Figure 9, with 1C constant current charge-discharge, after 300 circulations, Li
3v
2(PO
4)
3the capability retention of/C is 97%.
embodiment 12
By 4.52 g LiNO
3, 0.2828 g ZnSO
47H
2o is dissolved in the Mn (NO that 14.55 mL mass fractions are 50%
3)
2in the aqueous solution, stir about 4 h then dropwise drip the NH that concentration is 0.327 M in above-mentioned solution
4h
2pO
4the aqueous solution 20 mL, obtain colloidal sol.In this colloidal sol, add 0.0396 g sucrose.At room temperature, in this colloidal sol, dropwise drip 20 mL oxirane, the pH value of controlling colloidal sol over time rate (
pH/min) be 0.05 ~ 0.15, obtain the homodisperse jelly shape of each presoma component gel.By aging 240 h of this gel, then 60 ℃ of dry 24h in air, obtain LiMn
0.97zn
0.03pO
4presoma.Finally, at Ar/H
2(H in gaseous mixture
2volume fraction be 5%), 600 ℃ calcining 10 h obtain product LiMn
0.97zn
0.03pO
4/ C.
By the LiMn of preparation
0.97zn
0.03pO
4/ C positive electrode and acetylene black, PVDF are mixed to get slurry according to the ratio of mass ratio 75:15:10.Slurry is evenly coated on aluminium foil and obtains work electrode, take lithium sheet as to electrode, Celgard 2340 polypropylene screens are barrier film, 1 M LiPF
6/ EC+DMC (EC:DMC=1:1) is electrolyte, in being full of the glove box of argon gas, is assembled into button cell.
Above-mentioned battery is discharged and recharged and on instrument, carries out charge-discharge test at Land.Test result shows, product LiMn
0.97zn
0.03pO
4/ C can reversiblely discharge and recharge, and with 0.2C constant current charge-discharge, specific discharge capacity reaches 156 mAhg
-1.
embodiment 13
To the Mn (NO that pipettes 13 mL mass fraction 50 % in 150 mL beakers
3)
2the aqueous solution, then adds 10 mL deionized waters, 8.27 g LiNO successively
3, 2.40 g Cr (NO
3)
39H
2o and 10.2687 g sucrose, treat LiNO
3, after sucrose dissolves completely, dropwise add ethanolic solution 5 mL of the tetraethoxysilane that contains 0.06 moL.Under room temperature, dropwise add 30 mL expoxy propane, the pH value of controlling colloidal sol over time rate (
pH/min) be 0.2 ~ 0.6, obtain the equally distributed jelly shape of each presoma component gel.This gel, after aging one day, in 85 ℃ of dry 10 h, is obtained to LiMn
0.95cr
0.05siO
4presoma.Finally, at Ar/H
2(H in gaseous mixture
2volume fraction be 10%), 680 ℃ calcining 10 h obtain end-product LiMn
0.95cr
0.05siO
4/ C.
By the LiMn of preparation
0.95cr
0.05siO
4/ C positive electrode and acetylene black, PVDF are mixed to get slurry according to the ratio of mass ratio 75:15:10.Slurry is evenly coated on aluminium foil and obtains work electrode, take lithium sheet as to electrode, Celgard 2340 polypropylene screens are barrier film, 1 M LiPF
6/ EC+DMC (EC:DMC=1:1) is electrolyte, in being full of the glove box of argon gas, is assembled into button cell.
Above-mentioned battery is discharged and recharged and on instrument, carries out charge-discharge test at Land.Test result shows, product LiMn
0.95cr
0.05siO
4/ C has good chemical property, with 20 mAg
-1constant current charge-discharge, first discharge specific capacity reaches 200 mAh g
-1, approach theoretical specific capacity.
comparative example 1
Adopting polyethylene glycol (PEG-400) and citric acid is that gelling agent is prepared LiFePO
4/ C, with the LiFePO that adopts the inventive method to prepare
4compare.
By 16.16 g Fe (NO
3)
39H
2o, 4.0808 g lithium acetates, 8.4056 g citric acids are dissolved in 40 mL deionized waters, and stir about 1 h, then to the H that dropwise drips 3.92 g 85 % in above-mentioned solution
3pO
4, after stirring 1 h, add 16 g polyethylene glycol (PEG-400), then use ammoniacal liquor regulator solution pH to 8.5 ~ 9 of 25 %, then 50 ℃ of heating 6 h obtain gel.By after this gel drying, at Ar/H
2(H in gaseous mixture
2volume fraction be 10 %), 600 ℃ calcining 24 h obtain product LiFePO
4/ C.
By the LiFePO of preparation
4/ C, as anode material for lithium-ion batteries, is mixed to get slurry with acetylene black, PVDF according to the ratio of mass ratio 75:15:10.Slurry is evenly coated on aluminium foil and obtains work electrode, take lithium sheet as to electrode, Celgard 2340 polypropylene screens are barrier film, 1 M LiPF
6/ EC+DMC (EC:DMC=1:1) is electrolyte, in being full of the glove box of argon gas, is assembled into button cell.
Above-mentioned battery is discharged and recharged and on instrument, carries out charge-discharge test at Neware.The LiFePO that adopts this method to prepare
4the charging and discharging curve of/C provides in Figure 10, charging/discharging voltage scope 2.0 ~ 4.2 V, and while discharging and recharging with 0.2 C, specific discharge capacity is 101 mAhg
-1, be less than synthetic LiFePO in embodiment 1,2 and 4
4the specific discharge capacity of/C.
Claims (9)
1. the preparation method of polyanionic cathode material used for lithium ion battery, is characterized in that:
Concrete preparation process is:
1) lithium salts A and transition metal salt B are added in solvent C, the molar concentration that is made into A and B is respectively the solution D of 0.01～4M; Polyanion predecessor E is added in solvent F, be made into the solution G of molar concentration 0.01～4M;
2) press transition metal ions in transition metal salt B: in polyanion predecessor E, the mol ratio of polyanion is (0.9～1.5): (0.9～1.5), solution G is dropwise added in solution D, and add carbon source H simultaneously, obtain colloidal sol I, the molar concentration of carbon source H in colloidal sol I is 0.01～4M;
3) reaction temperature is constant in 10～50 ℃, under stirring condition, to step 2) drip in the colloidal sol I that makes or add organic epoxide in batches, by control, drip or add in batches the speed of organic epoxide, the pH value of control colloidal sol over time rate (Δ pH/min) is 0.01～4, obtains gel J;
4) after the gel J that step 3) made is aging, dry, make xerogel K;
5) xerogel K step 4) being made, in reducing atmosphere, in 400～1000 ℃ of calcining 0.5～24h, makes the nanoscale polyanion type positive electrode with good crystallinity;
Described organic epoxide is one or more in oxolane, oxirane, expoxy propane, epoxychloropropane, pyridine; And, to add in the process of organic epoxide, the pH value of control colloidal sol I over time rate (Δ pH/min) is 0.01～3.
2. according to preparation method claimed in claim 1, it is characterized in that: described lithium salts A is one or more in lithium sulfate, sulfuric acid monohydrate lithium, lithium acetate, lithium nitrate, nitrate trihydrate lithium, lithium dihydrogen phosphate, lithium chloride, a water lithium chloride;
Described transition metal salt B is one or more in the chloride, bromide, nitrate, dibasic alkaliine, dihydric phosphate, sulfate, acetate of I B, II B, III B, IV B, V B, VI B, VII B or VIII B transition metal ions;
Described polyanion precursor E is phosphoric acid, sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, lithium dihydrogen phosphate, three water ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, tetramethylsilane, tetraethyl silane, tetrapropyl silane, tetrabutyl silane, sodium metasilicate, silicic acid, silicon tetrachloride, siloxanes containing one or more in the compound of polyanion.
3. according to preparation method claimed in claim 2, it is characterized in that: described lithium salts A be lithium nitrate, nitrate trihydrate lithium, lithium dihydrogen phosphate, lithium chloride, a water lithium chloride, lithium acetate, in one or more;
One or more in the chloride that described transition metal salt B is Fe, Mn, Co, Ni, V, bromide, nitrate, sulfate, acetate;
Described polyanion precursor E is one or more in phosphoric acid, three water ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, tetramethylsilane, tetraethyl silane, tetrapropyl silane, tetrabutyl silane.
4. according to preparation method claimed in claim 1, it is characterized in that: solvent for use C or solvent F are respectively one or more in deionized water, methyl alcohol, absolute ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, propionitrile, formaldehyde, dimethyl formamide, ethylene glycol, propylene glycol, dimethyl sulfoxide (DMSO);
Described carbon source H is one or more in glucose, citric acid, sucrose, acetylene black, XC-72, BP-2000, super P, the molecular weight polyethylene glycol that is 200～20000, starch, cyclodextrin, polyacrylic acid;
Reducing atmosphere used is the gaseous mixture of one or both compositions in hydrogen and nitrogen or argon gas, and wherein, the volume content of hydrogen is 5～10%.
5. according to the preparation method described in claim 1 or 4, it is characterized in that: described carbon source H is one or more in glucose, citric acid, sucrose, acetylene black, XC-72, BP-2000, super P;
Reducing atmosphere used is the gaseous mixture that hydrogen and argon gas form, and wherein, the volume content of hydrogen is 5～10%.
6. according to preparation method claimed in claim 1, it is characterized in that: lithium salts A and transition metal salt B are added in solvent C, obtain solution D; In solution D, the mol ratio of lithium ion and transition metal ions is (0.9～2): (0.9～2).
7. according to preparation method claimed in claim 1, it is characterized in that: lithium salts A and the molar concentration of transition metal salt B in solution D are optimum with 1～3.5M respectively; Lithium ion in solution D and the mol ratio of transition metal ions are with 1～2.1 optimum; In solution D, the mol ratio of the polyanion in the transition metal ions in transition metal salt B and polyanion precursor E is with 1:(1～1.5) optimum.
8. according to preparation method claimed in claim 1, it is characterized in that: add in the process of organic epoxide, the temperature of constant colloidal sol is 15～30 ℃; Stir speed (S.S.) is 40～1000 revs/min.
9. according to preparation method claimed in claim 1, it is characterized in that: the calcining heat of xerogel K in reducing atmosphere is 600～900 ℃, calcination time is 2～20h.
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| "Characterization of Li2MnSiO4 and Li2FeSiO4 cathode materials synthesized via a citric acid assisted sol–gel method";C.Deng,et al.;《Materials Chemistry and Physics》;20100315;第120卷(第1期);14-17 * |
| "Synthesis and characterization of nano-sized LiFePO4 cathode;Kuei-Feng Hsu,et al.;《J . Ma t e r . C h em.》;20040701;第14卷;2690-2695 * |
| C.Deng,et al.."Characterization of Li2MnSiO4 and Li2FeSiO4 cathode materials synthesized via a citric acid assisted sol–gel method".《Materials Chemistry and Physics》.2010,第120卷(第1期),14-17. |
| Kuei-Feng Hsu,et al.."Synthesis and characterization of nano-sized LiFePO4 cathode.《J . Ma t e r . C h em.》.2004,第14卷2690-2695. |
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