CN102367170A - Core shell type carbon cladding nano-scale lithium iron phosphate compound cathode material and preparation method thereof - Google Patents
Core shell type carbon cladding nano-scale lithium iron phosphate compound cathode material and preparation method thereof Download PDFInfo
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- CN102367170A CN102367170A CN2011102889011A CN201110288901A CN102367170A CN 102367170 A CN102367170 A CN 102367170A CN 2011102889011 A CN2011102889011 A CN 2011102889011A CN 201110288901 A CN201110288901 A CN 201110288901A CN 102367170 A CN102367170 A CN 102367170A
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Abstract
The invention discloses a core shell type carbon cladding nano-scale lithium iron phosphate compound cathode material and a preparation method thereof. The preparation method is characterized by comprising the steps of: mixing a Fe<3+> compound, phosphoric acid, a doped element in a doped element salt solution, and an organic monomer according to a mol ratio to prepare a conductive macromolecule-cladded iron phosphate-doped element phosphate compound material; ball-grinding, drying and preforming the compound material, a lithium source compound and a conductive agent or conductive agent precursor according to a certain mol ratio after mixing to obtain a primarily-treated sheet precursor; roasting the primarily-treated sheet precursor at high speed, cooling, ball-grinding, drying and preforming to obtain a secondarily-treated sheet precursor; and after roasting the secondarily-treated sheet precursor, cooling to reach room temperature to obtain the core shell type carbon cladding nano-scale lithium iron phosphate compound cathode material. The core shell type carbon cladding nano-scale lithium iron phosphate compound cathode material has the advantages of easiness in control of components of raw materials and products, more uniform distribution of the conductive agent, easiness in control, low cost of the raw materials, and high purity of the synchronized lithium iron phosphate product.
Description
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries technical field, especially relate to a kind of hud typed secondary carbon-coated nano level iron phosphate compound anode material of lithium and preparation method thereof.
Background technology
Lithium ion battery is as a kind of high performance secondary green battery; Have high-voltage, high-energy-density (comprising volume energy, specific energy), low self-discharge rate, wide use temperature scope, long cycle life, environmental protection, memory-less effect and can high current charge-discharge etc. advantage, in various portable type electronic products, communication tool, electromobile and hybrid vehicle, obtained increasing application.In order to obtain heavy body, high-energy-density, the good high rate performance and the battery in cycle long life, positive electrode material has played important effect therein.Anode material for lithium-ion batteries has LiCoO
2, LiNiO
2And LiMn
2O
4Deng.LiCoO
2Be the positive electrode material that present commercialization lithium ion battery uses, it has high theoretical specific storage (274 mAh/g), excellent cycle performance; But its actual specific capacity has only about 140 mAh/g, when when charging lithium deviate from amount greater than 55%, material structure is destroyed and reduce its cycle performance; In addition; Cobalt is lower in natural abundance, and price is more expensive, and Co is that toxicity is bigger; For LiNiO
2The problem that exists is more, and it also has safety issue except synthetic difficulty and unstable under full-charge state.LiMn
2O
4Though application can solve LiCoO
2Price problem and LiNiO
2Safety-problems, but itself because Jahn-Teller effect cycle performance bad, restricted its application and development.Therefore, the positive electrode material that development of new high energy is cheap is most important to the development of lithium ion battery.
Iron lithium phosphate (LiFePO
4) have an olivine structural, can reversible ground doff lithium, and have specific storage height, good cycle, stable electrochemical property, lower-price characteristic, be first-selected new generation of green positive electrode material, particularly as the power lithium-ion battery material.But, present LiFePO
4Also there is following problem in positive electrode material:
(l) electronic conductivity and Li
+Spread coefficient is low.Low electronic conductivity and Li
+Spread coefficient causes the on the low side of the actual reversible capacity of material easily, influences high current charge-discharge ability and the low-temperature performance that reduces battery;
(2) control of purity is difficult.At LiFePO
4Building-up process in, Fe
2+At high temperature very easily be oxidized to Fe
3+Compound impurity, it is to LiFePO
4Chemical property has detrimentally affect.Even under strictness control preparation condition, this oxidation also difficulty is avoided, and conventional compound method need be used more expensive Fe
2+Compound is made source of iron, causes cost to increase;
(3) energy capacity of battery density is relatively low.LiFePO
4The theoretical density of material and actual tap density are more much lower than materials such as the sour lithium of cobalt, lithium manganate, nickel ternary cobalt manganic acid lithiums, cause LiFePO
4The loading level of material in battery is less relatively, thereby has reduced the energy density of battery.
Therefore, solve LiFePO
4Material low conductivity, low Li
+LiFePO in spread coefficient, low bulk density and the building-up process
4The problem of purity is LiFePO
4The key of positive electrode material practicability also is one of focus of Study on Li-ion batteries using.
At present, the method for synthesizing iron lithium phosphate mainly contains high-temperature solid phase reaction method, sol-gel method, hydrothermal method and chemistry and inserts the lithium method, in the above-mentioned existing compound method; High temperature solid-state method synthetic iron lithium phosphate particle diameter is bigger, and chemical property is not ideal enough, though hydrothermal method can be controlled particle diameter; But the difficulty of suitability for industrialized production is bigger, and sol-gel method is more satisfactory with the slotting lithium method synthetic iron lithium phosphate performance of chemistry, but its preparation technology is complicated; Production cycle is longer, and production cost is also higher.
Summary of the invention
Technical problem to be solved by this invention provides conducting polymer that a kind of direct employing prepares in advance, and to coat tertiary iron phosphate be source of iron; Adopt mechanical process for solid phase synthesis directly to synthesize purity height, the good hud typed secondary carbon-coated nano level iron phosphate compound anode material of lithium of chemical property, its preparation method can be controlled LiFePO effectively
4Chemical ingredients, phase composition and particle diameter, improve its homogeneity and conductivity, improve its chemical property, reduced material cost simultaneously, simplified synthesis technique, make it to be easy in industry, implement.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: a kind of preparation method of hud typed carbon-coated nano level iron phosphate compound anode material of lithium comprises the steps:
(1) be that 85% SPA is dissolved in the solvent with massfraction, and the pH value that adds the ammoniacal liquor regulator solution is 1～3, adding is used to form organic monomer, the Fe of conducting polymer then
3+Compound and alloying element salts solution obtain mixing solutions; With the mixing solutions stirring reaction 2～6h under 0～80 ℃ of condition that obtains; Filter then and obtain solid matter; It is till 6～8 as water white transparency and filtrating pH that solid matter is used a large amount of deionized waters or alcohol flushing to the color of filtrating, again in baking oven under 60～80 ℃ of conditions oven dry 24 h, obtain the tertiary iron phosphate-alloying element phosphate composite material that coats by conducting polymer;
After taking by weighing by certain mol proportion, tertiary iron phosphate-alloying element phosphate composite material, Li source compound and static eliminator that (2) will be coated by conducting polymer or static eliminator presoma put into ball grinder; And add 4/5 of alcohol solvent to ball grinder volume; Ball milling 1～6h in high energy ball mill; Oven dry, compressing tablet gets primary treatment sheet presoma;
(3) primary treatment sheet presoma is placed high temperature sintering furnace, at N
2, Ar, N
2With H
2Mixed gas or Ar and H
2In the atmosphere of mixed gas, with the heating rate intensification of 5～30 ℃/min, in 300～500 ℃ of constant temperature calcining 3～5 h; Be cooled to room temperature with 1～20 ℃/min rate of temperature fall then, with cooled sample ball milling 1～6 h once more, oven dry; Compressing tablet obtains secondary treatment sheet presoma, wherein N
2With H
2Mixed gas and Ar and H
2H in the mixed gas
2Volume ratio is respectively 5%～10%;
(4) secondary treatment sheet presoma is placed high temperature sintering furnace, at N
2, Ar, N
2With H
2Mixed gas or Ar and H
2In the atmosphere of mixed gas, the heating rate intensification with 5～30 ℃/min in 650～800 ℃ of constant temperature calcining 15～20 h, is cooled to room temperature with 1～20 ℃/min rate of temperature fall then, promptly obtains hud typed two carbon-coated nano level iron phosphate compound anode material of lithium.
Solvent described in the step (1) is deionized water, absolute ethyl alcohol, terepthaloyl moietie or glycerine.
Fe described in the step (1)
3+Compound: phosphoric acid: the alloying element in the alloying element salts solution: the mol ratio of organic monomer is 1～2:2:0～1:1～5.
Described Fe
3+Compound is iron nitrate, iron acetate, iron(ic)chloride or ironic citrate.
Salts solution in the described alloying element salts solution is nitrate salt, acetate, chlorate or Citrate trianion, and wherein alloying element is Mn
3+, Co
3+, Ni
3+, Ca
2+, Mg
2+Or Zn
2+
The organic monomer of described formation conducting polymer is aniline, pyrroles or thiophene.
In the step (2), described by the iron in the tertiary iron phosphate-alloying element phosphate composite material of conducting polymer coating and the common molar weight of alloying element: the molar weight of the elemental lithium in the described Li source compound: the molar weight of described static eliminator or static eliminator presoma is 1.0:0.90～1.0:0.1～5.
Described Li source compound is at least a in Quilonum Retard, Lithium Acetate, Lithium Hydroxide MonoHydrate, Trilithium phosphate and the lithium nitrate.
Described static eliminator is at least a in Graphite Powder 99, carbon black and the acetylene black; Described static eliminator presoma is at least a in sucrose, glucose, starch, formaldehyde-resorcinol resin, carbon gel, SEPIGEL 305 and the Vestolen PP 7052.
The present invention also comprises the iron phosphate compound anode material of lithium that is formed by method for preparing.
The present invention machinery process for solid phase synthesis prepares and prevents the reunion of nanometer powder in the tertiary iron phosphate discharge process and grow up to improving LiFePO
4The conductive capability of nanometer powder is most important, and the present invention mainly prevents the reunion of nanometer powder through following measure and grows up and improve nanometer LiFePO
4The conductive capability of powder: (1) coats the hard aggregation that one deck conducting polymer composite prevents nanoparticle in the follow-up heat treatment process on the surface of presoma tertiary iron phosphate; (2) thickness of shell electroconductive polymer layer is big to the agglomeration influence, is the reunion that 10～1000 nm prevent particle in presoma preparation and the drying course through the thickness of optimizing the conducting polymer coating layer therefore; (3) have the static eliminator of reductive agent effect or the conductivity that the static eliminator presoma improves material concurrently through adding in synthetic; (4) static eliminator or static eliminator presoma have secondary carbon coating LiFePO
4Effect is at LiFePO
4Nanometer powder surface secondary coats carbon-coating and can further suppress nanoparticle generation repolymerization in the charge and discharge process.
The present invention takes following measure to improve conductivity of electrolyte materials:
(1) takes to reduce the material granule size, shorten the evolving path of lithium ion in material, thereby improve the rate of diffusion of lithium ion in material;
(2) employing adds the organic reaction monomer that can form conducting polymer among the present invention in precursor solution, at Fe
3+Initiation under, the monomer polymerization reaction take place is coated on FePO
4The surface, hindered FePO
4Particulate is grown up, and reaches the purpose that improves conductivity of electrolyte materials;
(3) behind adding lithium source and static eliminator or the static eliminator presoma, in heat treatment process, the carbon in-site secondary that static eliminator or the cracking of static eliminator presoma generate is coated on the iron lithium phosphate particle surface, further reaches the purpose that improves the iron lithium phosphate conductivity; (4) element doping is introduced heteroatoms in material lattice, thereby the heteroatoms ionic exists the conduction that can promote lithium ion to improve conductivity of electrolyte materials.
Compared with prior art, the invention has the advantages that: hud typed secondary carbon-coated nano level iron phosphate compound anode material of lithium of the present invention and preparation method thereof has following advantage:
(1) the trivalent tertiary iron phosphate that directly uses conducting polymer to coat is source of iron; Avoided ferrous lithium synthesis step loaded down with trivial details in other synthetic technologys; Solved the impure problem of product that often has among the conventional preparation method of the ferrous salt raw material that in air, is prone to oxidation of using; Conducting polymer coats the particle diameter that can effectively control the tertiary iron phosphate presoma, and (conducting polymer is coated on the surface of tertiary iron phosphate particle; Can effectively prevent further growing up of iron phosphate grains), and then can reduce title product LiFePO
4Particle diameter, particle diameter is more little, it is just low more to react needed temperature, energy expenditure is just more little, and the LiFePO that obtains
4Cycle performance and conductivity and stability can improve synthetic LiFePO of the present invention greatly
4/ C material and metal lithium sheet are assembled into test battery, and with the charging of 0.2C multiplying power, when the 0.2C multiplying power discharging, reversible specific capacity reaches 161mAh/g, and specific storage reaches 150 mAh/g when the 1C multiplying power discharging, and shows outstanding cyclical stability;
(2) specific discharge capacity of product can be controlled through changing processing parameter flexibly: can control the size of lithium iron phosphate nano particle and the thickness of shell static eliminator owing to change processing parameter, so the specific discharge capacity of product also is able to fine control;
(3) Chemical Composition of product, phase composition and even particle size distribution and control easily can directly be synthesized the nano-powder of particle diameter less than 100 nm;
(4) coating of shell carbon-coating can strengthen the electroconductibility between iron lithium phosphate particle and the iron lithium phosphate particle, reduces the polarization of battery;
(5) the sp2 hydridization carbon atom of conducting polymer high-temperature carbonization formation can be LiFePO
4Electron tunnel is provided, with compensation Li
+The charge balance (tertiary iron phosphate at high temperature react the process that generates iron lithium phosphate in make the conducting polymer high-temperature carbonization that is coated on the tertiary iron phosphate outside form sp2 hydridization carbon atom) of process is taken off in embedding.
In sum; The present invention utilizes mechanical process for solid phase synthesis to prepare the method for hud typed carbon-coated nano level iron phosphate compound anode material of lithium; Material composition and product prescription are controlled easily, static eliminator more even distribution (form because static eliminator is conducting polymer and the sucrose high temperature cabonization that is coated on the nanoparticle outside, the carbon that forms after the carbonization is evenly distributed on the skin of material) and control easily; The cost of material that uses is cheap; Synthetic iron lithium phosphate product purity is high, and chemical property is good, and preparation technology is simple, flow process is short, easy to control, easy realization industriallization.
Description of drawings
Fig. 1 is for pressing the prepared LiFePO of embodiment 1
4The X-ray diffracting spectrum of/C nano composite material;
Fig. 2 is for pressing the prepared LiFePO of embodiment 1
4The stereoscan photograph of/C (amplifying 10000 times);
Fig. 3 is for to press embodiment 1 prepared lithium ion battery charging and discharging curve, and voltage range 2.5-4.2V, electrolytic solution are 1 mol L
-1LiPF
6EC+DEC (1:1, volume ratio) solution, charging and discharging currents is 34 mA/g (0.2 C), 85 mA/g (0.5 C), 170 mA/g (1 C), 340 mA/g (2 C), 850 mA/g (5 C);
Fig. 4 is for pressing the cycle characteristics figure of embodiment 1 prepared lithium ion battery, and voltage range 2.5-4.2V, electrolytic solution are 1 mol L
-1LiPF
6EC+DEC (1:1, volume ratio) solution, charging and discharging currents is 34 mA/g (0.2 C), 85 mA/g (0.5 C), 170 mA/g (1 C), 340 mA/g (2 C), 850 mA/g (5 C).
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
One embodiment
Embodiment 1
The SPA that takes by weighing 46 grams 85% is dissolved in the 200 mL deionized waters, and the pH value that adds the ammoniacal liquor regulator solution is 2, adds 37 gram aniline then, with the 2 mol L that prepare in advance
-1Fe (NO
3)
3 Solution 100 mL dropwise join in the above-mentioned solution; Mixing solutions stirring reaction 6 h under 60 ℃ of conditions that obtain; Filter then and obtain solid matter; With solid matter use a large amount of deionized water rinsings totally to the color of filtrating be till 6～8 as water white transparency and filtrating pH, in baking oven, in 60 ℃ of constant temperatures under, dry 24 h and obtain hud typed tertiary iron phosphate/polyaniline composite material; Hud typed tertiary iron phosphate/the polyaniline composite material of 4.77 grams, 2.70 gram acetate dihydrate lithiums and 1.32 gram sucrose are put into ball grinder after taking by weighing; With ethanol solvent (add ethanol volume to ball grinder volume 4/5) ball milling 2 h in high energy ball mill; Oven dry; Compressing tablet gets primary treatment sheet presoma; Primary treatment sheet presoma is placed high temperature sintering furnace, at N
2In the atmosphere, heat up,, be cooled to room temperature with 10 ℃/min rate of temperature fall then in 400 ℃ of constant temperature calcining 4 h with 10 ℃/min heating rate; With above-mentioned cooled sample ball milling 2 h once more, oven dry, compressing tablet, secondary treatment sheet presoma; Secondary treatment sheet presoma is placed high temperature sintering furnace, at N
2In the atmosphere, heat up, in 700 ℃ of constant temperature calcining 15 h, be cooled to room temperature with 10 ℃/min rate of temperature fall then, obtaining hud typed secondary carbon-coated nano level iron phosphate compound anode material of lithium behind the finished product ball milling with 10 ℃/min heating rate.Fig. 1 X-ray diffraction analytical results shows that prepared iron phosphate powder is olivine-type LiFePO
4There is not impurity peaks in phase structure in the spectrogram, product purity is high.Fig. 2 is LiFePO
4/ C powder amplifies 10000 times electromicroscopic photograph, and the product particle size is basically less than 100 nm.
LiFePO with nucleocapsid structure
4/ C nano composite material and acetylene black and sticker (PTFE) add absolute ethyl alcohol by the 85:10:5 mass ratio to be mixed well, and makes the electrode slice that quality is about 8 mg, and 120 ℃ of following dry 24 h in a vacuum.Making positive pole with above-mentioned electrode slice, is negative pole with the metal lithium sheet, and PP SHEET FOR OPP TAPE is a barrier film, 1 mol L
-1LiPF
6EC+DEC (1:1; Volume ratio) solution is made electrolytic solution; In being full of the glove box of argon gas, be assembled into button cell, the LAND battery test system that Lan Nuo Electronics Co., Ltd. produces in Wuhan under normal temperature is made the constant current charge-discharge loop test, and charging and discharging currents density respectively is 0.2 C, 0.5 C, 1 C, 2 C, 5 C; Final discharging voltage 2.5 V, end of charge voltage 4.2 V.Accompanying drawing 3 is a different multiplying battery charging and discharging curve.Visible by figure, it is 3.34-3.40V at 0.2 C multiplying power discharging voltage that the present invention makes LiFePO 4 material, and reversible specific capacity is 95% of theoretical specific capacity up to 161 mAh/g.Cycle performance of battery is also very outstanding, and the cycle performance of battery with 0.2 C, 0.5 C, 1 C, 2 C, 5 C rate charge-discharges is shown in accompanying drawing 4 respectively.
Embodiment 2
The SPA that takes by weighing 46 grams 85% is dissolved in the 200 mL deionized waters, and the pH value that adds the ammoniacal liquor regulator solution is 2, adds 37 gram aniline then, with the 2 mol L that prepare in advance
-1Fe (NO
3)
3 Solution 100 mL dropwise join in the above-mentioned solution; Mixing solutions stirring reaction 6 h under 60 ℃ of conditions that obtain; Filter then and obtain solid matter; With solid matter use a large amount of deionized water rinsings totally to the color of filtrating be till 6～8 as water white transparency and filtrating pH, in baking oven, in 60 ℃ of constant temperatures under, dry 24 h and obtain hud typed tertiary iron phosphate/polyaniline composite material; Hud typed tertiary iron phosphate/the polyaniline composite material of 4.77 grams, 2.70 gram acetate dihydrate lithiums and 4.98 gram sucrose are put into ball grinder after taking by weighing; With ethanol solvent (add ethanol volume to ball grinder volume 4/5) ball milling 2 h in high energy ball mill; Oven dry; Compressing tablet gets primary treatment sheet presoma; Primary treatment sheet presoma is placed high temperature sintering furnace, at N
2In the atmosphere, heat up,, be cooled to room temperature with 10 ℃/min rate of temperature fall then in 400 ℃ of constant temperature calcining 4 h with 10 ℃/min heating rate; With above-mentioned cooled sample ball milling 2 h once more, oven dry, compressing tablet, secondary treatment sheet presoma; Secondary treatment sheet presoma is placed high temperature sintering furnace, at N
2In the atmosphere, heat up, in 700 ℃ of constant temperature calcining 15 h, be cooled to room temperature with 10 ℃/min rate of temperature fall then, obtaining hud typed secondary carbon-coated nano level iron phosphate compound anode material of lithium behind the finished product ball milling with 10 ℃/min heating rate.
Embodiment 3
The SPA that takes by weighing 23 grams 85% is dissolved in the 400 mL deionized waters, and the pH value that adds the ammoniacal liquor regulator solution is 2, adds 30 gram aniline then, with the 2 mol L that prepare in advance
-1Fe (NO
3)
3 Solution 100 mL dropwise join in the above-mentioned solution; Mixing solutions stirring reaction 4 h under 80 ℃ of conditions that obtain; Filter then and obtain solid matter; With solid matter use a large amount of deionized water rinsings totally to the color of filtrating be till 6～8 as water white transparency and filtrating pH, in baking oven, in 80 ℃ of constant temperatures under, dry 24 h and obtain hud typed tertiary iron phosphate/polyaniline composite material; Hud typed tertiary iron phosphate/the polyaniline composite material of 4.17 grams, 2.04 gram acetate dihydrate lithiums and 1.10 gram sucrose are put into ball grinder after taking by weighing; With ethanol solvent (add ethanol volume to ball grinder volume 4/5) ball milling 4 h in high energy ball mill; Oven dry; Compressing tablet gets primary treatment sheet presoma; Primary treatment sheet presoma is placed high temperature sintering furnace, at N
2In the atmosphere, heat up,, be cooled to room temperature with 10 ℃/min rate of temperature fall then in 450 ℃ of constant temperature calcining 4 h with 20 ℃/min heating rate; With above-mentioned cooled sample ball milling 4 h once more, oven dry, compressing tablet, secondary treatment sheet presoma; Secondary treatment sheet presoma is placed high temperature sintering furnace, at N
2In the atmosphere, heat up, in 750 ℃ of constant temperature calcining 15 h, be cooled to room temperature with 20 ℃/min rate of temperature fall then, obtaining hud typed secondary carbon-coated nano level iron phosphate compound anode material of lithium behind the finished product ball milling with 20 ℃/min heating rate.
Embodiment 4
The SPA that takes by weighing 23 grams 85% is dissolved in the 400 mL deionized waters, and the pH value that adds the ammoniacal liquor regulator solution is 2, adds 30 gram pyrroles then, with the 2 mol L that prepare in advance
-1Fe (NO
3)
3 Solution 100 mL dropwise join in the above-mentioned solution; Mixing solutions stirring reaction 4 h under 80 ℃ of conditions that obtain; Filter then and obtain solid matter; With solid matter use a large amount of deionized water rinsings totally to the color of filtrating be till 6～8 as water white transparency and filtrating pH, in baking oven, in 60 ℃ of constant temperatures under, dry 24 h and obtain hud typed tertiary iron phosphate/polyaniline composite material; Hud typed tertiary iron phosphate/the polyaniline composite material of 4.47 grams, 2.04 gram acetate dihydrate lithiums and 1.10 gram sucrose are put into ball grinder after taking by weighing; With ethanol solvent (add ethanol volume to ball grinder volume 4/5) ball milling 4 h in high energy ball mill; Oven dry; Compressing tablet gets primary treatment sheet presoma; Primary treatment sheet presoma is placed high temperature sintering furnace, at N
2In the atmosphere, heat up,, be cooled to room temperature with 10 ℃/min rate of temperature fall then in 400 ℃ of constant temperature calcining 4 h with 10 ℃/min heating rate; With above-mentioned cooled sample ball milling 4 h once more, oven dry, compressing tablet, secondary treatment sheet presoma; Secondary treatment sheet presoma is placed high temperature sintering furnace, at N
2In the atmosphere, heat up, in 700 ℃ of constant temperature calcining 15 h, be cooled to room temperature with 10 ℃/min rate of temperature fall then, obtaining hud typed secondary carbon-coated nano level iron phosphate compound anode material of lithium behind the finished product ball milling with 20 ℃/min heating rate.
Embodiment 5
The SPA that takes by weighing 23 grams 85% is dissolved in the 400 mL deionized waters, and the pH value that adds the ammoniacal liquor regulator solution is 2, adds 30 gram aniline then, with the 0.5 mol L for preparing in advance
-1Fe (NO
3)
3And 1.5 mol L
-1Mn (NO
3)
3Solution 100 mL dropwise join in the above-mentioned solution; Mixing solutions stirring reaction 4 h under 80 ℃ of conditions that obtain; Filter then and obtain solid matter; Use a large amount of deionized water rinsings totally to the color of filtrating be till 6～8 as water white transparency and filtrating pH, in baking oven, in 80 ℃ of constant temperatures under, dry 24 h and obtain hud typed tertiary iron phosphate-manganous phosphate/polyaniline composite material; Hud typed tertiary iron phosphate/the polyaniline composite material of 4.95 grams, 2.64 gram acetate dihydrate lithiums and 2.15 gram sucrose are put into ball grinder after taking by weighing; With ethanol solvent (add ethanol volume to ball grinder volume 4/5) ball milling 4 h in high energy ball mill; Oven dry; Compressing tablet gets primary treatment sheet presoma; Primary treatment sheet presoma is placed high temperature sintering furnace, at N
2In the atmosphere, heat up,, be cooled to room temperature with 10 ℃/min rate of temperature fall then in 450 ℃ of constant temperature calcining 4 h with 20 ℃/min heating rate; With above-mentioned cooled sample ball milling 4 h once more, oven dry, compressing tablet, secondary treatment sheet presoma; Secondary treatment sheet presoma is placed high temperature sintering furnace, at N
2In the atmosphere, heat up, in 750 ℃ of constant temperature calcining 15 h, be cooled to room temperature with 20 ℃/min rate of temperature fall then, obtaining hud typed secondary carbon-coated nano level iron phosphate compound anode material of lithium behind the finished product ball milling with 20 ℃/min heating rate.
Embodiment 6
The SPA that takes by weighing 23 grams 85% is dissolved in the 400 mL deionized waters, and the pH value that adds the ammoniacal liquor regulator solution is 2, adds 30 gram aniline then, with the 1 mol L for preparing in advance
-1Fe (NO
3)
3And 1 mol L
-1CoCl
3Solution 100 mL dropwise join in the above-mentioned solution; Mixing solutions stirring reaction 4 h under 80 ℃ of conditions that obtain; Filter then and obtain solid matter; With solid matter use a large amount of deionized water rinsings totally to the color of filtrating be till 6～8 as water white transparency and filtrating pH, in baking oven, in 80 ℃ of constant temperatures under, dry 24h and obtain hud typed tertiary iron phosphate-cobaltous phosphate/polyaniline composite material; 4.84 gram hud typed tertiary iron phosphate-cobaltous phosphate/polyaniline composite materials, 2.44 gram acetate dihydrate lithiums and 1.68 gram sucrose are put into ball grinder after taking by weighing; With ethanol solvent (add ethanol volume to ball grinder volume 4/5) ball milling 4 h in high energy ball mill; Oven dry; Compressing tablet gets primary treatment sheet presoma; Primary treatment sheet presoma is placed high temperature sintering furnace, at N
2In the atmosphere, heat up,, be cooled to room temperature with 20 ℃/min rate of temperature fall then in 450 ℃ of constant temperature calcining 4 h with 20 ℃/min heating rate; With above-mentioned cooled sample ball milling 4 h once more, oven dry, compressing tablet, secondary treatment sheet presoma; Secondary treatment sheet presoma is placed high temperature sintering furnace, at N
2In the atmosphere, heat up, in 750 ℃ of constant temperature calcining 15 h, be cooled to room temperature with 20 ℃/min rate of temperature fall then, obtaining hud typed secondary carbon-coated nano level iron lithium phosphate-cobalt phosphate lithium composite positive pole behind the finished product ball milling with 20 ℃/min heating rate.
The foregoing description is a detailed description of the invention, and protection scope of the present invention is not limited to the described technical scheme of above-mentioned embodiment, and should be as the criterion with the described protection domain of claim.
Claims (10)
1. the preparation method of a hud typed carbon-coated nano level iron phosphate compound anode material of lithium is characterized in that preparation process is following:
(1) be that 85% SPA is dissolved in the solvent with massfraction, and the pH value that adds the ammoniacal liquor regulator solution is 1～3, adding is used to form organic monomer, the Fe of conducting polymer then
3+Compound and alloying element salts solution obtain mixing solutions; With the mixing solutions stirring reaction 2～6h under 0～80 ℃ of condition that obtains; Filter then and obtain solid matter; It is till 6～8 as water white transparency and filtrating pH that solid matter is used a large amount of deionized waters or alcohol flushing to the color of filtrating, again in baking oven under 60～80 ℃ of conditions oven dry 24 h, obtain the tertiary iron phosphate-alloying element phosphate composite material that coats by conducting polymer;
After taking by weighing by certain mol proportion, tertiary iron phosphate-alloying element phosphate composite material, Li source compound and static eliminator that (2) will be coated by conducting polymer or static eliminator presoma put into ball grinder; And add 4/5 of alcohol solvent to ball grinder volume; Ball milling 1～6h in high energy ball mill; Oven dry, compressing tablet gets primary treatment sheet presoma;
(3) primary treatment sheet presoma is placed high temperature sintering furnace, at N
2, Ar, N
2With H
2Mixed gas or Ar and H
2In the atmosphere of mixed gas, with the heating rate intensification of 5～30 ℃/min, in 300～500 ℃ of constant temperature calcining 3～5 h; Be cooled to room temperature with 1～20 ℃/min rate of temperature fall then, with cooled sample ball milling 1～6 h once more, oven dry; Compressing tablet obtains secondary treatment sheet presoma, wherein N
2With H
2Mixed gas and Ar and H
2H in the mixed gas
2Percent by volume is respectively 5%～10%;
(4) secondary treatment sheet presoma is placed high temperature sintering furnace, at N
2, Ar, N
2With H
2Mixed gas or Ar and H
2In the atmosphere of mixed gas, the heating rate intensification with 5～30 ℃/min in 650～800 ℃ of constant temperature calcining 15～20 h, is cooled to room temperature with 1～20 ℃/min rate of temperature fall then, promptly obtains hud typed two carbon-coated nano level iron phosphate compound anode material of lithium.
2. the preparation method of hud typed carbon-coated nano level iron phosphate compound anode material of lithium according to claim 1 is characterized in that: the solvent described in the step (1) is deionized water, absolute ethyl alcohol, terepthaloyl moietie or glycerine.
3. the preparation method of hud typed carbon-coated nano level iron phosphate compound anode material of lithium according to claim 1 is characterized in that: the Fe described in the step (1)
3+Compound: phosphoric acid: the alloying element in the alloying element salts solution: the mol ratio of organic monomer is 1～2:2:0～1:1～5.
4. the preparation method of hud typed carbon-coated nano level iron phosphate compound anode material of lithium according to claim 3 is characterized in that: described Fe
3+Compound is iron nitrate, iron acetate, iron(ic)chloride or ironic citrate.
5. the preparation method of hud typed carbon-coated nano level iron phosphate compound anode material of lithium according to claim 3; It is characterized in that: the salts solution in the described alloying element salts solution is nitrate salt, acetate, chlorate or Citrate trianion, and wherein alloying element is Mn
3+, Co
3+, Ni
3+, Ca
2+, Mg
2+Or Zn
2+
6. the preparation method of hud typed carbon-coated nano level iron phosphate compound anode material of lithium according to claim 3 is characterized in that: the organic monomer of described formation conducting polymer is aniline, pyrroles or thiophene.
7. according to the preparation method of claim 1 or 6 described hud typed carbon-coated nano level iron phosphate compound anode material of lithium; It is characterized in that: in the step (2), described by the iron in the tertiary iron phosphate-alloying element phosphate composite material of conducting polymer coating and the common molar weight of alloying element: the molar weight of the elemental lithium in the described Li source compound: the molar weight of described static eliminator or static eliminator presoma is 1.0:0.90～1.0:0.1～5.
8. the preparation method of hud typed carbon-coated nano level iron phosphate compound anode material of lithium according to claim 7 is characterized in that: described Li source compound is at least a in Quilonum Retard, Lithium Acetate, Lithium Hydroxide MonoHydrate, Trilithium phosphate and the lithium nitrate.
9. the preparation method of hud typed secondary carbon-coated nano level iron phosphate compound anode material of lithium according to claim 7 is characterized in that: described static eliminator is at least a in Graphite Powder 99, carbon black and the acetylene black; Described static eliminator presoma is at least a in sucrose, glucose, starch, formaldehyde-resorcinol resin, carbon gel, SEPIGEL 305 and the Vestolen PP 7052.
10. the iron phosphate compound anode material of lithium of processing according to the preparation method of each described hud typed carbon-coated nano level iron phosphate compound anode material of lithium among the claim 1-9.
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