CN101393982B - Method for producing carbon coated nano stage lithium iron phosphate by precipitation - Google Patents
Method for producing carbon coated nano stage lithium iron phosphate by precipitation Download PDFInfo
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Abstract
The invention discloses a precipitation method for preparing nanometer level iron phosphate lithium coated with carbon. The method comprises the following steps: firstly, weighing iron salt, deionized water and a compound of metallic elements; after the stirring and the mixing are performed, adding a phosphorous compound and citric acid diluted with water to the mixture; after the stirring is performed again, adding a precipitation agent to the mixture and controlling to the neutrality; stirring to react in a container, and after the static placement, respectively adding the deionized water, a carbon source and lithium salt to mix uniformly after the precipitate is filtered and washed; stirring again to react, and drying the water at 30 to 160 DEG C and warming up at the heating rate under the protection of non-oxidized gas after a product is crashed; baking at a constant temperature of 450 to 850 DEG C, cooling down to a room temperature at a cooling rate or with a stove, and finally obtaining the nanometer level ferric phosphate lithium coated with the carbon after crashing is performed. The precipitation method has the advantage that the raw material cost and the processing cost are low because bivalent iron is taken as the raw material. The iron phosphate lithium prepared by using the process has the characteristics of good physical processing performance and good electrochemistry performance, and is suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of preparation method of battery material, the liquid-phase precipitation preparation method of the nano-scale lithium iron phosphate of the doped with metal elements that a kind of carbon of saying so more specifically coats.
Background technology
Reported LiFePO first from 1997
4Had since the removal lithium embedded function phosphate of olivine type class intercalation materials of li ions LiMPO
4(Co Ni), receives much attention as very potential anode material for lithium-ion batteries for M:Mn, Fe.Wherein theoretical capacity is the LiFePO of 170mAh/g
4,, be considered to the most promising anode material for lithium-ion batteries with characteristics such as its abundant iron resource, cheap price, good thermal stability and environmental friendliness.
The method of synthesizing iron lithium phosphate has high-temperature solid phase reaction method, liquid phase co-electrodeposition method, sol-gal process, hydro thermal method, liquid phase oxidation reducing process, solid phase microwave method and mechanical ball milling method at present.Widely used high-temperature solid phase reaction method ([J] A.K.Padihi et al Journal of the electrochemical Society for example, Vo1 144,1188-1194 (1997), [J] A.Yamada et al Journal of the electrochemicalSociety, Vol148, A960 one A967 (2001), US5910382, CN1958441A and CN1401559A) be with ferrous salt such as ferric acetate or ferric oxalate class, mix with ammonium hydrogen phosphate and lithium salts such as lithium carbonate or lithium hydroxide, in inert atmosphere such as nitrogen or argon gas, through the synthetic LiFePO4 of 300-800 ℃ of roastings.Its reaction equation is:
Li
2CO
3+2Fe(CH
3COO)
2+2NH
4H
2PO
4
→LiFePO
4+4NH
3+CO
2+5H
2O+2CH
3COOH
Discharge ammonia in this method course of reaction, and be difficult to obtain pure LiFePO
4
Adopt liquid-phase coprecipitation among the patent WO 02/083555A2, under the control pH value, codeposition goes out ferrous phosphate and lithium phosphate presoma from corresponding salting liquid, and this presoma is made LiFePO 650-800 ℃ of roastings
4And the Li (Fe that mixes in the iron position
xM (1)
yM (2)
z) PO
4(wherein, x is 0.5～1, and y is 0～0.5, and z is 0～0.5, and x+y+z=1; Or x is 0, and y is 1, and z is 0; M (1) and M (2) are a kind of among Sc, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Be, Mg, Ca, Sr, Ba, Al, Zr, the La).Whole process of preparation all is to carry out in nitrogen protection atmosphere, is unfavorable for industrialization.
CN1800003 is by LiFePO with ferrous iron source compound, P source compound and oxidant
4Stoichiometric proportion mix, control Ph=1-8, filter the reaction back, washing, oven dry obtain the FePO about 100nm
4Presoma is then with FePO
4Presoma is placed in the stove with Li source compound and reducing agent mixing, in calcining at constant temperature, makes LiFePO in non-oxidizing atmosphere
4
The CN1632970 its preparation method is earlier with ferrous sulfate, phosphorus source, complexing agent or add manganese sulfate therein again; be made into mixture aqueous solution after mixing in proportion; again with ammonia spirit reaction synthesizing spherical ferrous ammonium phosphate or manganese phosphate ferrous ammonium presoma; evenly mix with mol ratio with lithium carbonate at 1: 1 the dry back of washing; under nitrogen atmosphere protection, obtained LiFePO4 or the iron manganese phosphate for lithium that average grain diameter is 7-12 μ m in high-temperature heat treatment 8-48 hour through 600-900 ℃.
When CN1431147A prepares the presoma of LiFePO4 with liquid-phase coprecipitation, adopt closed container, removed nitrogen protection atmosphere from, the presoma that makes roasting in 500-800 ℃ of non-oxidizing atmospheres made the lithium iron phosphate nano powder in 5-48 hours.First capacity is in 130-147mAh/g scope when the 0.5C constant current discharge for the LiFePO 4 material that this patent system gets, and 40 circulation back capacity attenuation degree are 3% one 7%.But it is a kind of in aluminium, boron, magnesium, calcium, hydrogen, sodium, titanium, barium, vanadium, chromium, manganese, cobalt, copper, the zinc doping element only.
CN101150191 is characterized in that molecular formula is LiM
xFe
1-xPO
4(M is La or Ac, 0.01≤x≤0.05) has olivine structural; Preparation process is: with lithium compound, molysite, phosphate, lanthanum or actinium compound are raw material, and by atomic ratio Li: Fe: P: La (or Ac)=1: (1-x): 1: x adds that wet-milling is placed on N in the ball mill
2, H
2Pre-burning in the mixed-gas atmosphere; And then after wet-milling and the drying, dry ball milling again is then at N
2, H
2Carry out secondary clacining in the mixed-gas atmosphere
F.Croce etc. are at [J] Electrochemical and Solid-State Letters, and 5 (3), utilize sol-gel method to prepare LiFePO among A47 one A50 (2002)
4Material.Be about to LiOH and Fe (NO
3) 3 add in the ascorbic acid solutions, and then and H
3PO
4Solution mixes.Regulate pH value with ammoniacal liquor, make gel 60 ℃ of heating.This gel is through 350 ℃ of nitrogen atmospheres, and after the heat treatment in 12 hours, again through 800 ℃, roast prepared LiFePO in 24 hours
4This method is not used more expensive ferrous organic salt, and utilizes ascorbic acid with Fe
3+Be reduced to Fe
2+, technical process is trouble.Chinese patent CN1410349A sol-gel method is with Fe (Ac)
2, LiAc, NH
4H
2PO
4With organic acid such as tartaric acid be raw material, under logical condition of nitrogen gas, 80-100 ℃ of conditions make gel, this gel is under 350-800 ℃ of reducing atmospheres, roasting obtains LiFePO
4Powder.This patent prepares the overall process of LiFePO4, comprises raw material Fe (Ac)
2Preparation, all be in logical nitrogen or reducing gases atmosphere, to carry out inconvenient operation.
Hydro thermal method mainly is that the employing autoclave is a reaction vessel, and precursor solution is directly synthesized LiFePO through high-temperature high-voltage reaction
4At document [J] Electrochemistry Communications, in 3 (2001), 505-508, adopt FeSO as Y.S.Yang etc.
4, P
2O
5With LiOH be raw material, synthesized LiFePO in 170 ℃, 3 days hydro-thermal reactions
4Open wait quietly document [J] (battery, 35 (6), 2005,425-426) with FeSO
47H
2O, phosphoric acid and LiOH.H
2O is a raw material, and after reacting 6 hours under 190 ℃ of high-temperature and high-pressure conditions, filtration washing adds 0.1667 times glucose again, calcines down at 600 ℃ and gets LiFePO in 3 hours
4Hydrothermal synthesis method need use high-pressure reaction vessel, and is unfavorable to suitability for industrialized production.
A kind of with in the oxidants hydrogen peroxide, sodium peroxide, potassium permanganate, potassium chlorate of Chinese patent CN1805181A, ferrous salt is oxidized to high ferro with phosphorus lithium liquid phase reactor, and be doped with a kind of in titanium, vanadium, chromium, manganese, cobalt, nickel, copper, zinc, zirconium, Niobium, molybdenum, the chromium element, oxidant is heated or sees the easy decomposition explosion of light, the improper suitability for industrialized production of this method.
Masashi Higuchi etc. are in [J] Journal of power sources119-121,2003 (6), 258-261, with Li
2CO
3, NH
4H
2PO
4And Fe (CH
3COO)
2Or Fe (CH
3CHOHCOO)
22H
2O is that raw material synthesizes LiFePO with microwave method
4This synthetic method is simple, but the synthetic product chemical property in the document is desirable not enough.Wang Xiaojian etc. (Chinese Journal of Inorganic Chemistry, 2005,21 (2), 249-253) adopt household microwave oven to synthesize carbon dope LiFePO4 positive electrode, in microwave oven heating process in order to prevent that sample from by sampleization, covering sample with graphite powder.Li Faxi etc. (the journal .2005 of University of Science ﹠ Technology, Beijing, 27 (1), 86-89) adopt microwave-assisted synthesis to synthesize reason ion battery positive electrode LiFePO4, and carry out carbon and mix, synthesize composite L iFePO
4/ C.(Electrochem.Commun.2003, (5): 839-842) with (NH such as K.S.Park
4)
2FeSO
4.6H
2O, H
3PO
4Synthetic in LiOH solution, through filtration, drying, add the carbon dust of high-ratio surface, high temperature is made LiFePO in microwave oven
4Powder.CN1775666 takes by weighing lithium carbonate, ferrous oxalate and ammonium dihydrogen phosphate by stoichiometric proportion, an amount of thermal conducting agent and the organic substance that is used to carry out the carbon coating, make the abundant ground and mixed of dispersant with absolute ethyl alcohol, be pressed into bulk after drying, put into the crucible that active carbon is housed, crucible is placed the microwave field radiation heating, can make mutually the evenly LiFePO4 of carbon coating.The method of this employing microwave radiation device fabrication LiFePO4, industrial being difficult to implements.
LiFePO
4Being a kind of very promising anode material for lithium-ion batteries, having very outstanding advantage, is hot research in recent years.But also there are shortcomings such as the low and ions diffusion poor performance of conductance in it, and the former can solve by adding conductive agent, and the LiFePO of synthetic small particle diameter is then depended in the latter's improvement
4The village high greatly [J] (China YouSe Acta Metallurgica Sinica, 2005,15 (12): 2034-2039.) with FeSO
4, H
3PO
4With LiOH be raw material, adopt the synthetic high nanometer LiFePO of purity that obtained of hydro thermal method
4, and after polypropylene cracking carbon coats processing, reach 163mAh/g with the 0.05C reversible capability of charging and discharging, and discharging and recharging with 0.5C, reversible capacity still has 144mAh/g.Yang Wei etc. [J] (material engineering, 2005,6:36-40) prepared the single olivine-type LiFePO of modification with coprecipitation
4Positive electrode is the nanometer rods shape, has good electrochemical, with 0.2mA/cm
2Current density discharge, first discharge specific capacity reaches 142.3mAh/g, still keeps 129.7mAh/g behind the cycle charge-discharge 20 times.But the LiOH that these two kinds of research institutes use all wants excessive twice, and waste of raw materials is big.For this reason, the production small particle diameter nano-scale lithium iron phosphate material of exploitation low consumption lithium salts just seems particularly necessary.
Summary of the invention
1. invent the technical problem that will solve
Weak point at the said method existence, the invention provides the method that a kind of precipitation method prepare the nano-scale lithium iron phosphate of carbon coating, directly adopting divalent iron salt, phosphorus-containing compound and lithium salts is raw material, and, avoided mixing in other synthetic methods uneven shortcoming with the directly synthetic good LiFePO 4 material of chemical property of liquid phase synthesis process.
Further purpose of the present invention be add contain metallic element compound in reactant, can prepare the LiFePO 4 material of the better doping metals of performance.
2. technical scheme
Technical scheme of the present invention is as follows:
A kind of precipitation method prepare the method for the nano-scale lithium iron phosphate of carbon coating, and its step is as follows:
(1) divalent iron salt, pure water citric acid being mixed the back adds in the phosphorus-containing compound of dilute with water, stirring the back once more adds precipitation reagent and controls PH4～8, stirring reaction is 0.5～24 hour in the container at normal temperatures, leave standstill 0～48 hour after, this sediment of filtration washing;
(2) adding deionized water, dissolved organic carbon source and lithium salts respectively in above-mentioned sediment mixes; control PH4～8; stirring reaction after 0.5～24 hour once more in the container at normal temperatures; dry moisture down at 30～160 ℃; product is pulverized the back to heat up with 1～30 ℃/min rate of heat addition under the non-oxidizing gas protection; in 450～850 ℃ of constant temperature roast 30～600min; then with 1～30 ℃/min cooling rate or cool to normal temperature with the furnace, through behind the comminution by gas stream the nano-scale lithium iron phosphate (Li that coats of carbon
xA
yFePO
4) product (wherein: x+y=1, A are Sc, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Be, Mg, Ca, Sr, Ba, Al, Zr, one or more in La, Nb, Mo, Cd, Y, Ce, La, Ac, Sn, Sb, Na and the elements such as w).
Compound and divalent iron salt, pure water, the citric acid that will contain metallic element in the above-mentioned steps (1) mix in the phosphorus-containing compound of back adding dilute with water.
Control pH value wherein, stirring reaction, time of repose, these reaction conditions require not strict, as long as in rational reaction range; Same heat temperature raising and cooling are so same.
Above-mentioned described divalent iron salt is one or more in ferrous sulfate, frerrous chloride, ferrous oxalate or the ferrous acetate.Above-mentioned phosphorus-containing compound is one or more in ammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate, lithium dihydrogen phosphate or the phosphoric acid.The described lithium salts of step (2) is one or more in lithium acetate, lithium hydroxide, lithium oxalate, lithium carbonate, lithium dihydrogen phosphate or the lithium phosphate.
Non-oxidizing gas described in the above-mentioned steps (2) is one or more in hydrogen, argon gas, nitrogen, carbon monoxide, carbon dioxide or the ammonia.Dissolved organic carbon source described in the step (2) is one or more in glucose, sucrose, fructose or the lactose.Precipitation reagent described in the step (1) is one or more in NaOH, sodium carbonate, sodium acid carbonate, dibastic sodium phosphate, potassium hydroxide, potash, potassium phosphate, potassium hydrogen phosphate, ammoniacal liquor, ammonia, carbonic hydroammonium, ammonium carbonate, ammonium phosphate, ammonium hydrogen phosphate, urea, lithium hydroxide or the lithium carbonate.
Metallic element in its above the compound that contains metallic element: the lithium in the lithium salts: the iron in the molysite: the ratio of the amount of substance of the phosphorus in the phosphorus-containing compound is 0.001～0.06:0.94～0.999:1:1, and wherein contain metallic element in the compound of metallic element and the lithium amount of substance sum in the lithium salts: the iron in the molysite: the ratio of the amount of substance of the phosphorus in the phosphorus-containing compound is 1:1:1; The carbon source consumption is 1～40% of a LiFePO4 quality; The citric acid consumption is 1～25% of a LiFePO4 quality.
The present invention uses the ball mill container that is of pulverizing, is selected from stainless steel jar mill, agate jar, polyurethane ball grinder, tungsten carbide ball milling jar, corundum ball grinder.
3. beneficial effect
The invention provides the method that a kind of precipitation method prepare the nano-scale lithium iron phosphate of carbon coating, compare existing preparation method, have following obvious usefulness: (1) directly uses ferrous iron to be source of iron, has avoided ferrous salt synthesis step loaded down with trivial details in other synthetic technologys; (2) material composition of the present invention and product prescription are controlled easily, and synthetic LiFePO4 product chemical property is good.The LiFePO that the present invention synthesizes
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 150mAh/g, this product average grain diameter 70nm, and tap density can reach 1.5g/cm
3(3) LiFePO4 synthetic method of the present invention, lithium source consumption is little, and technology is simple to operation, and the raw material that uses is large chemical products, easily realizes the commercial scale cleaner production, and is with low cost.
Embodiment
Further specify the present invention below in conjunction with embodiment.
Embodiment 1:LiFePO
4/ C's is synthetic
27.8 gram (0.1 mole) ferrous sulfate, 300 gram deionized water and stirring are mixed the back add 11.50 gram (0.1 mole) ammonium dihydrogen phosphates, stir the back once more and add 6 gram citric acids, and adding ammoniacal liquor control PH5.5, stirring reaction is 5 hours in 30 ℃ container, after leaving standstill 15 hours, this sediment of filtration washing.
Adding 200 gram deionized waters, 5 gram glucose and 4.2 gram (0.1 mole) lithium hydroxides in this sediment respectively mixes; stirring reaction after 4 hours once more in 30 ℃ container; dry moisture down at 100 ℃; product is pulverized the back to heat up with the 10 ℃/min rate of heat addition under nitrogen protection; in 725 ℃ of constant temperature roast 600min; cool to room temperature then with the furnace, get lithium iron phosphate nano level product through after pulverizing.
Make battery and test: use the positive electrode coating of oiliness system to being synthesized, surface density is controlled at 100～110g/m
2Take by weighing 0.8 restrain iron phosphate powder, add the polyvinylidene fluoride binding agent that 0.1 gram acetylene black and 0.1 gram are dissolved in the N.N=methyl pyrrolidone, be applied to after mixing and make positive plate on the aluminium foil.In the argon gas atmosphere dry glove box, with metal lithium sheet is to electrode, and Celgard2700 is a barrier film, ethylene carbonate (EC)+carbonic acid diformazan～(DMC)/IMLiPF6 is an electrolyte, be assembled into the CR2016 button cell, leave standstill and allow abundant wetting barrier film of electrolyte and both positive and negative polarity more than 6 hours.Then on the charge-discharge test instrument with the 0.2C constant-current constant-voltage charging.
This product average grain diameter 80nm, tap density can reach 1.26g/cm
3, first discharge specific capacity can reach 123mAh/g under the room temperature.
Embodiment 2: the LiFePO of doped metallic elements Mg
4/ C's is synthetic
27.8 gram (0.1 mole) ferrous sulfate and 400 gram deionized water and stirring mixing backs are added 11.50 gram (0.1 mole) ammonium dihydrogen phosphates, add 0.246 gram (0.001 mole) MgSO after stirring once more
4.7H
2O continue to stir add adds 4 gram citric acids, and adds ammoniacal liquor control PH7.2, and stirring reaction is 2 hours in 50 ℃ container, leave standstill 5 hours after, this sediment of filtration washing.
Adding 600 gram deionized waters, 5 gram glucose and 4.16 gram (0.099 mole) lithium hydroxides in this sediment respectively mixes; stirring reaction after 4 hours once more in 50 ℃ container; dry moisture down at 90 ℃; product is pulverized the back to heat up with the 10 ℃/min rate of heat addition under nitrogen protection; in 650 ℃ of constant temperature roast 600min; cool to room temperature then with the furnace, get lithium iron phosphate nano level product through after pulverizing.This product average grain diameter 110nm, tap density can reach 1.4g/cm
3, first discharge specific capacity can reach 143mAh/g under the room temperature.
Embodiment 3: the LiFePO of doped metallic elements Mn and W
4/ C's is synthetic
With the gram of 0.246 among the embodiment 2 (0.001 mole) MgSO
4.7H
2O changes 0.0017 gram (0.00001 mole) MnSO into
4.H
2O and 0.13 gram (0.00099 mole) ammonium tungstate, other preparation proportionings and operating procedure make metallic element Mn and W doped iron phosphate lithium nanoscale product with embodiment 2.
Prepare button cell by embodiment 1 method, and test its cycle performance of battery.This product average grain diameter 70nm, tap density can reach 1.5g/cm
3, first discharge specific capacity can reach 150mAh/g under the room temperature.
Embodiment 4: the LiFePO of doped metallic elements Zr and W
4/ C's is synthetic
27.8 gram (0.1 mole) ferrous sulfate and 400 gram deionized water and stirring mixing backs are added 11.50 gram (0.1 mole) ammonium dihydrogen phosphates, add 0.00356 gram (0.00001 mole) Zr (SO after stirring once more
4)
2.4H
2O and 0.13 gram (0.00099 mole) ammonium tungstate continue to stir add add 3.5 gram citric acids, and add ammoniacal liquor control PH6.8, and stirring reaction is 4 hours in 70 ℃ container, leave standstill 10 hours after, this sediment of filtration washing.
Adding 600 gram deionized waters, 5 gram glucose and 4.16 gram (0.099 mole) lithium hydroxides in this sediment respectively mixes; stirring reaction after 4 hours once more in 40 ℃ container; dry moisture down at 120 ℃; product is pulverized the back to heat up with the 10 ℃/min rate of heat addition under nitrogen protection; in 700 ℃ of constant temperature roast 300min; cool to room temperature then with the furnace, through getting the lithium iron phosphate nano level product of doped metallic elements Zr and W after pulverizing.Prepare button cell by embodiment 1 method, and test its cycle performance of battery.This product average grain diameter 120nm, tap density can reach 1.4g/cm
3, first discharge specific capacity can reach 145mAh/g under the room temperature.
Embodiment 5: the LiFePO of doped metallic elements Al and Ca
4/ C's is synthetic
0.1 mole of frerrous chloride and 400 gram deionized water and stirring are mixed back adding 0.1 mole of phosphoric acid hydrogen ammonium, stir the back once more and add 0.0001 mole of AlCl
3With 0.0002 mole of CaCl of gram
2, continue to stir add add 10 gram citric acids, and add ammoniacal liquor control PH4～8, stirring reaction is 24 hours in 50 ℃ container, leave standstill 48 hours after, this sediment of filtration washing.
Adding 600 gram deionized waters, 15 gram glucose and 0.097 mole of lithium carbonate in this sediment respectively mixes; stirring reaction after 2 hours once more in 50 ℃ container; dry moisture down at 90 ℃; product is pulverized the back to heat up with the 2 ℃/min rate of heat addition under nitrogen protection; in 650 ℃ of constant temperature roast 600min; cool to room temperature then with the furnace, get lithium iron phosphate nano level product through after pulverizing.This product average grain diameter 100nm, tap density can reach 1.4g/cm
3, first discharge specific capacity can reach 153mAh/g under the room temperature.
Embodiment 6
With the gram of 0.246 among the embodiment 2 (0.001 mole) MgSO
4.7H
2O changes 0.0034 gram (0.00001 mole) MnSO into
4.H
2O and 0.13 gram (0.00099 mole) ammonium tungstate, the amount of citric acid is 60 grams, and 5 gram glucose change 40 gram fructose and lactose into, and other preparation proportionings and operating procedure make metallic element Mn and W doped iron phosphate lithium nanoscale product with embodiment 2.
Embodiment 7
With 0.0001 mole of AlCl among the embodiment 5
3With 0.0002 mole of CaCl of gram
2Change 0.003 mol sulfuric acid copper and 0.003 mol sulfuric acid zinc into, continue to stir add 10 gram citric acids, add ammoniacal liquor control PH4～8, stirring reaction is 24 hours in 50 ℃ container, leave standstill 48 hours after, this sediment of filtration washing.
Adding 600 gram deionized waters, 15 gram glucose and 0.094 mole of lithium carbonate in this sediment respectively mixes; stirring reaction after 2 hours once more in 50 ℃ container; dry moisture down at 160 ℃; product is pulverized the back to heat up with the 30 ℃/min rate of heat addition under argon shield; in 850 ℃ of constant temperature roast 600min; cool to room temperature then with the furnace, get lithium iron phosphate nano level product through after pulverizing.
Claims (9)
1. the precipitation method prepare the method for the nano-scale lithium iron phosphate that carbon coats, and its step is as follows:
(1) divalent iron salt, pure water and citric acid being mixed the back adds in the phosphorus-containing compound of dilute with water, phosphorus-containing compound wherein is one or more in ammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate, lithium dihydrogen phosphate or the phosphoric acid, stirring back adding precipitation reagent once more and controlling PH is 4～8, stirring reaction is 0.5～24 hour in the container at normal temperatures, after leaving standstill 0～48 hour, this sediment of filtration washing;
(2) adding deionized water, dissolved organic carbon source and lithium salts respectively in above-mentioned sediment mixes; control PH is 4～8; stirring reaction after 0.5～24 hour once more in the container at normal temperatures; dry moisture down at 30～160 ℃; product is pulverized the back to heat up with 1～30 ℃/min rate of heat addition under the non-oxidizing gas protection; in 450～850 ℃ of constant temperature roast 30～600min; then with 1～30 ℃/min cooling rate or cool to normal temperature with the furnace, through behind the comminution by gas stream the nano-scale lithium iron phosphate that coats of carbon.
2. a kind of precipitation method according to claim 1 prepare the method for the nano-scale lithium iron phosphate of carbon coating, it is characterized in that compound and divalent iron salt, pure water, the citric acid that will contain metallic element in the step (1) mix in the phosphorus-containing compound of back adding dilute with water.
3. a kind of precipitation method according to claim 2 prepare the method for the nano-scale lithium iron phosphate of carbon coating, it is characterized in that divalent iron salt described in the step (1) is one or more in ferrous sulfate, frerrous chloride, ferrous oxalate or the ferrous acetate.
4. a kind of precipitation method according to claim 3 prepare the method for the nano-scale lithium iron phosphate that carbon coats, and it is characterized in that metallic element in the step (1) is one or more in Sc, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Be, Mg, Ca, Sr, Ba, Al, Zr, La, Nb, Mo, Cd, Y, Ce, La, Ac, Sn, Sb, Na or the W element.
5. prepare the method for the nano-scale lithium iron phosphate of carbon coating according to each described a kind of precipitation method in the claim 2～4, it is characterized in that the described lithium salts of step (2) is one or more in lithium acetate, lithium hydroxide, lithium oxalate, lithium carbonate, lithium dihydrogen phosphate or the lithium phosphate.
6. prepare the method for the nano-scale lithium iron phosphate of carbon coating according to each described a kind of precipitation method in the claim 2～4, it is characterized in that the non-oxidizing gas described in the step (2) is one or more in hydrogen, argon gas, nitrogen, carbon monoxide, carbon dioxide or the ammonia.
7. prepare the method for the nano-scale lithium iron phosphate of carbon coating according to each described a kind of precipitation method in the claim 2～4, it is characterized in that the dissolved organic carbon source described in the step (2) is one or more in glucose, sucrose, fructose or the lactose.
8. prepare the method for the nano-scale lithium iron phosphate of carbon coating according to each described a kind of precipitation method in the claim 2～4, it is characterized in that the precipitation reagent described in the step (1) is one or more in NaOH, sodium carbonate, sodium acid carbonate, dibastic sodium phosphate, potassium hydroxide, potash, potassium phosphate, potassium hydrogen phosphate, ammoniacal liquor, ammonia, carbonic hydroammonium, ammonium carbonate, ammonium phosphate, ammonium hydrogen phosphate, urea, lithium hydroxide or the lithium carbonate.
9. the method for preparing the nano-scale lithium iron phosphate of carbon coating according to each described a kind of precipitation method in the claim 2～4, it is characterized in that the metallic element in the described compound that contains metallic element: the lithium in the lithium salts: the iron in the molysite: the ratio of the amount of substance of the phosphorus in the phosphorus-containing compound is 0.001～0.06: 0.94～0.999: 1: 1, wherein contain metallic element in the compound of metallic element and the lithium amount of substance sum in the lithium salts: the iron in the molysite: the ratio of the amount of substance of the phosphorus in the phosphorus-containing compound was 1: 1: 1; The carbon source consumption is 1～40% of a LiFePO4 quality; The citric acid consumption is 1～25% of a LiFePO4 quality.
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| CN2008101950557A CN101393982B (en) | 2008-10-28 | 2008-10-28 | Method for producing carbon coated nano stage lithium iron phosphate by precipitation |
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