CN101635352A - Method for preparing anode material of carbon-coated lithium ion battery - Google Patents
Method for preparing anode material of carbon-coated lithium ion battery Download PDFInfo
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- CN101635352A CN101635352A CN200910304569A CN200910304569A CN101635352A CN 101635352 A CN101635352 A CN 101635352A CN 200910304569 A CN200910304569 A CN 200910304569A CN 200910304569 A CN200910304569 A CN 200910304569A CN 101635352 A CN101635352 A CN 101635352A
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- H—ELECTRICITY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention discloses a method for preparing an anode material of a carbon-coated lithium ion battery. The anode material confirms to the general formula C-LixM(1-y)M'y(XO4)n, wherein x is larger than 0 and smaller than or equal to 2; y is larger than or equal to 0 and smaller than or equal to 0.5, and n is larger than or equal to 1 and smaller than or equal to 1.5; M is a transition metal element; M' is selected from Mg, Ti, Cr, V or Al; and X is selected from S, P or Si. The method for preparing an anode material of a carbon-coated lithium ion battery comprises the following steps: (1) weighing a lithium compound, an M compound, an M' compound, an X compound and at least one inorganic conductive carbon according to a certain proportion; adding solvent and then carrying out ball-milling processing; then atomizing and granulating to obtain a precursor; (2) preburning the precursor at 200-500 DEG C for 2-10 hours at protective atmosphere of gases and then resintering at 500-800 DEG C for 2-24 hours; (3) cooling a product obtained in the step (2) to room temperature and then pulverizing. The anode material has high electrical conductivity and has the characteristics of high specific capacity and favorable multiplying power discharge.
Description
Technical field
The invention belongs to the lithium ion battery field, be specifically related to a kind of preparation method of anode material of carbon-coated lithium ion battery.
Background technology
Lithium ion battery has the voltage height as the new generation of green high-energy battery, and energy density is big, good cycle, and self discharge is little, memory-less effect, advantage such as operating temperature range is wide and being widely used.Positive electrode is again the important component part of lithium ion battery, and traditional Postive electrode material of li-ion accumulator concentrates on the transition metal oxide such as the LiMO of lithium
2(M=Co, Ni, Mn) and LiMn
2O
4But LiCoO
2The cost height, natural resources shortage, overcharge resistance performance is poor; LiNiO
2The preparation difficulty, poor heat stability; LiMn
2O
4Aboundresources, low price, nontoxic, but its capacity is lower, and high-temperature stability and cyclical stability are relatively poor.
General formula LiMPO with olivine structural
4The insertion compound be known, wherein M belongs to first row transition metal, such as the metal ion of Mn, Fe, Co or Ni; When keeping same olivine structural basically, a part of phosphorus can be replaced such as elements such as Si, S.
In the above-mentioned options that might be used for lithium rechargeable battery, because LiFePO as positive electrode
4Raw material sources are extensive, cheap, non-environmental-pollution, the Heat stability is good of material, the security performance of prepared battery is outstanding, makes it in various removable field of power supplies, particularly the required large-sized power field of power supplies of electric motor car has great market prospects, this large-sized power power supply is low to the volume and capacity ratio requirement of material, and material price, fail safe and environmental-protecting performance are had relatively high expectations, thereby makes LiFePO
4Become the anode material for lithium-ion batteries of new generation of tool development and application potentiality.
The LiFePO of olivine-type structure
4Major advantage with respect to cobalt acid lithium, LiMn2O4, lithium nickelate is this material Heat stability is good, and between the electrolyte highly compatible is arranged and have higher security performance, however the LiFePO of pure phase
4It is low by (10 to exist a significant disadvantages-conductivity
-9S.m
-1About), electron conduction and lithium ion migration rate are very slow, have restricted the performance of its electrical property, can't directly be used for lithium ion battery as positive electrode.
In order to address this problem, industry mainly improves its conductivity by following several approach at present:
Scheme one is the WO1997040541 that the University of Texas had, and the method that WO 2006130766 patent families are adopted is characterized in that raw material except selecting lithium source, phosphorus source and divalence source of iron for use, has also added organic substance as carbon source, at the synthetic LiFePO of high temperature
4Process in, organic substance decomposes synchronously, makes C be coated on LiFePO
4Material surface, improve the conductivity of material with this, effect is fairly obvious, emits a large amount of gas but adopt in the building-up process of the method because raw material and organic carbon source all acutely decompose, and exists weightless big, input-output ratio is low, product porosity height, tap density is low, and granularity is little, the pattern of product is irregular, and batch stability is difficult to shortcomings such as control.
Scheme two is characterized in that raw material except selecting lithium source, phosphorus source and ferric iron source for use for the US7422823B2 patent of Valence company application, has also added inorganic conductive carbon, with C reduction ferric iron under the high temperature, synthetic LiFePO
4Material is coated on material surface with C simultaneously, improves the conductivity of material with this.This method technology is simple, only produce a small amount of gas in the building-up process, weightless little, the input-output ratio height, the tap density height, granularity is moderate, pattern is easy to control, batch good stability, but exist gram volume relatively low in the synthetic process of product of this method as the actual use of positive electrode, shortcoming such as high rate performance is relatively poor relatively.
Scheme three is the WO 2007030816 of A123 company application, US 20070190418 patents, the method that does not adopt C to coat, but pass through doped metal ion, while control material pattern makes the nanoscale product and improves conductivity, but the nanoscale LiFePO that this method is synthesized
4Material cost is high, poor in processability when making battery pole piece.
Summary of the invention
The shortcoming of aspects such as, multiplying power discharging low that exists at above-mentioned prior art and poor safety performance such as material poorly conductive, specific capacity, the purpose of this invention is to provide a kind of preparation method of anode material for lithium-ion batteries of new coating carbon, make the material of acquisition possess good discharge performance, specific capacity height, multiplying power discharging and the good characteristics of security performance.
For realizing purpose of the present invention, the inventor provides following technical proposals:
A kind of preparation method of anode material of carbon-coated lithium ion battery comprises the steps: successively
1. Li compound, M compound, M ' compound, X compound and at least a inorganic conductive carbon are mixed, the gained mixture is done ball-milling treatment after adding solvent, the ball milling product obtains presoma through mist projection granulating, wherein, the mol ratio of Li in the described mixture: M: M ': X=0.95～1.05: 0.45～1.05: 0～0.55: 0.95～1.05, the inorganic conductive carbon content is 1～20wt%;
2. under the Buchholz protection atmosphere, presoma 200～500 ℃ of pre-burnings 2～10 hours, was then handled 2～24 hours at 500～800 ℃ of following double sinterings;
3. treat step 2. products therefrom be cooled to and do pulverizing after the room temperature and can obtain general molecular formula C-Li
xM
1-yM '
y(XO
4)
nMaterial,
Wherein, 0＜x≤2,0≤y≤0.5,1≤n≤1.5, M is a transition metal, and M ' is selected among Mg, Ti, Cr, V or the Al at least a, and X is selected from S, P or Si.
The inventor discovers the above-mentioned Li compound of the raw material selection of lithium ion anode material, M compound, M ' compound, X compound, as lithium source, phosphorus source and divalence source of iron, and add inorganic conductive carbon as conductive agent, the gained mixture is forced moulding through granulation after by even ball milling again, can regulate and control the pattern of product, inorganic conductive carbon is uniformly distributed among the precursor; Inorganic conductive carbon and Li in the follow-up sintering process
xM
1-yM '
y(XO
4)
nProduce well crosslinked, thereby improved the conductivity of material.Method of the present invention has overcome the shortcoming of several schemes described in the background technology, the C-Li for preparing
xM
1-yM '
y(XO
4)
nMaterial is as LiFePO
4Material has outstanding combination property.
As preferred version,, a kind of in M compound chosen from Fe, manganese, cobalt or the nickel salt of its step in 1. according to preparation method of the present invention.
As preferred version, according to preparation method of the present invention, when the M compound of its step described in 1. selected molysite for use, molysite referred to divalent iron salt, preferably selects oxalic acid molysite or acetic acid molysite for use.
As preferred version, according to preparation method of the present invention, the Li compound of its step in 1. is selected from lithium carbonate, lithium hydroxide, lithium dihydrogen phosphate, lithium acetate or the lithium nitrate at least a.More preferably at least a in lithium carbonate, lithium hydroxide or the lithium acetate.
As preferred version, according to preparation method of the present invention, the inorganic conductive carbon of its step in 1. is selected from behind native graphite, Delanium micro mist, carbon black granules, acetylene black particle, carbon nano-tube, carbon nano-fiber or the organic substance high temperature pyrolysis at least a in the resulting DIC.
As preferred version, according to preparation method of the present invention, above-mentioned organic substance is selected from one or more the mixture in the polymer that contains carbon skeleton and oligomer, simple carbohydrate or polymer and the aromatic hydrocarbon based organic compound.
As preferred version, according to preparation method of the present invention, above-mentioned organic substance is selected from polyvinyl alcohol, butadiene-styrene rubber breast, carboxymethyl cellulose, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile, phenolic resins, epoxy resin, glucose, sucrose, fructose, cellulose or the starch at least a.
As preferred version, according to preparation method of the present invention, the solvent of its step in 1. is selected from least a in deionized water, ethanol, ethylene glycol, propyl alcohol, isopropyl alcohol, n-butanol, glycerine or the ethylenediamine.More preferably at least a in deionized water, ethanol or the ethylene glycol.
As preferred version, according to preparation method of the present invention, the mist projection granulating of its step in 1. adopts centrifugal spray granulating and drying machine.
As preferred version, according to preparation method of the present invention, the gas of its step in 2. is at least a in hydrogen, nitrogen or the argon gas.The mixture of nitrogen or hydrogen or its arbitrary proportion more preferably.
As preferred version, according to preparation method of the present invention, the pre-burning of its step in 2. is to handle 4～8 hours down at 300～500 ℃.
As preferred version, according to preparation method of the present invention, the double sintering of its step in 2. is to handle 5-20 hour down at 550～780 ℃.
As preferred version, according to preparation method of the present invention, micronizer, airslide disintegrating mill, mechanical type pulverizer or compound pulverizer are adopted in the pulverizing of its step in 3..More preferably adopt micronizer or compound pulverizer.
Compared with prior art, the present invention has the following advantages:
The inventive method is simple to operate, and cost is lower; The C-Li that makes
xM
1-yM '
y(XO
4)
nIts good conductivity of material, structure is single, does not contain dephasign, and material has the good characteristics of specific capacity height, multiplying power discharging and security performance, is suitable for electrokinetic cell; Its preparation method is easy to suitability for industrialized production.
Description of drawings
Fig. 1 is the crystalline phase figure of the material of embodiment 1 preparation; (2 μ m, * 6000 times.)
Fig. 2 is the XRD diffracting spectrum of the material of embodiment 1 preparation.
Fig. 3 is the charging and discharging curve figure of the material of embodiment 1 and comparative example preparation, wherein ,-▲-be example 1 material 0.2C discharge curve ,-◆-comparative example material 0.2C discharge curve,
Be example 1 material 0.2C charging curve ,-●-be comparative example material 0.2C charging curve.
Fig. 4 is the 0.2C cyclic curve figure of the material of embodiment 1 preparation.
Fig. 5 is the multiplying power discharging curve of the material of embodiment 1 preparation, wherein,
Be the 15C discharge curve ,-▲-be the 8C discharge curve ,-●-be the 5C discharge curve ,-◆-be the 3C discharge curve,
Be the 1C discharge curve ,-★-be the 0.3C discharge curve.
Fig. 6 is the multiplying power discharging curve of the material of comparative example preparation, wherein,
Be the 15C discharge curve ,-▲-be the 8C discharge curve ,-●-be the 5C discharge curve ,-★-be the 3C discharge curve ,-◆-be the 1C discharge curve, be the 0.3C discharge curve.
Embodiment
Below in conjunction with embodiment, be described more specifically content of the present invention.Should be appreciated that enforcement of the present invention is not limited to the following examples, all will fall into protection range of the present invention any pro forma accommodation and/or the change that the present invention made.
In the present invention, if not refer in particular to, all part, percentages are unit of weight, and all equipment and raw material etc. all can be buied from market or the industry is commonly used.
With 5mol Li
2CO
3, 10mol FeC
2O
42H
2O, 10mol (NH
4)
2HPO
4, 3000ml ethanol and 100g carbon nano-tube join in the ball grinder, adds the diameter 10mm zirconia ball of milling simultaneously, ball milling is 8 hours under the 350r/min rotating speed, obtains uniform paste mixture material; Use 200 ℃ of spray dryings of centrifugal spray granulating and drying machine then, obtain presoma; Above-mentioned presoma is put into the atmosphere protection tube furnace, feed nitrogen,, be warmed up to 700 ℃ and constant temperature then 6 hours, naturally cool to room temperature in 400 ℃ of insulation 3h down; Above-mentioned material is joined micronizer pulverize, the gained crushed material is crossed 300 order reciprocating sieves in 100 ℃ of dryings after 10 hours, obtain C-LiFePO
4Product.
Embodiment 2
With the 10mol lithium hydroxide, 10mol ferrous acetate, 10mol NH
4H
2PO
4, 3000ml deionized water and 160g acetylene black join in the ball grinder, add the diameter 8mm zirconia ball of milling simultaneously, and ball milling is 6 hours under the 300r/min rotating speed, obtains uniform paste mixture material; Use 180 ℃ of spray dryings of centrifugal spray granulating and drying machine then, obtain presoma; Above-mentioned presoma is put into the atmosphere protection tube furnace, feed nitrogen and hydrogen (volume ratio 97: 3),, be warmed up to 600 ℃ and constant temperature then 12 hours, naturally cool to room temperature in 380 ℃ of insulation 8h down; Above-mentioned material is joined micronizer pulverize, the gained crushed material is crossed 300 order reciprocating sieves in 110 ℃ of dryings after 6 hours, obtain C-LiFePO
4Product.
Embodiment 3
10mol lithium acetate, 10mol ferrous ammonium phosphate, 3500ml ethanol and 200g phenolic resin heat are separated the carbon that obtains to join in the ball grinder, add the diameter 10mm zirconia ball of milling simultaneously, ball milling is 6 hours under the 350r/min rotating speed, obtains uniform paste mixture material; Use 250 ℃ of spray dryings of centrifugal spray granulating and drying machine then, obtain presoma; Above-mentioned presoma is put into the atmosphere protection tube furnace, feed nitrogen,, be warmed up to 800 ℃ and constant temperature then 8 hours, naturally cool to room temperature in 350 ℃ of insulation 8h down; Above-mentioned material is joined micronizer pulverize, the gained crushed material is crossed 300 order reciprocating sieves in 100 ℃ of dryings after 15 hours, obtain C-LiFePO
4Product.
Embodiment 4
With 3mol lithium carbonate, 4mol lithium acetate, 10mol ferrous acetate, 10mol (NH
4)
3PO
4, 4000ml ethanol and 50g carbon nano-fiber join in the ball grinder, adds the diameter 8mm zirconia ball of milling simultaneously, ball milling is 8 hours under the 380r/min rotating speed, obtains uniform paste mixture material; Use 200 ℃ of spray dryings of centrifugal spray granulating and drying machine then, obtain presoma; Above-mentioned presoma is put into the atmosphere protection tube furnace, feed nitrogen,, be warmed up to 600 ℃ and constant temperature then 10 hours, naturally cool to room temperature in 450 ℃ of insulation 6h down; Above-mentioned material is joined micronizer pulverize, the gained crushed material is crossed 300 order reciprocating sieves in 120 ℃ of dryings after 4 hours, obtain C-LiFePO
4Product.
Embodiment 5
With 5mol Li
2CO
3, 10mol ferrous ammonium phosphate, 3000ml ethylene glycol and 160g carbon nano-tube join in the ball grinder, adds the diameter 10mm zirconia ball of milling simultaneously, ball milling is 10 hours under the 300r/min rotating speed, obtains uniform paste mixture material; Use 200 ℃ of spray dryings of centrifugal spray granulating and drying machine then, obtain presoma; Above-mentioned presoma is put into the atmosphere protection tube furnace, feed nitrogen,, be warmed up to 700 ℃ and constant temperature then 12 hours, naturally cool to room temperature in 400 ℃ of insulation 8h down; Above-mentioned material is joined micronizer pulverize, the gained crushed material is crossed 300 order reciprocating sieves in 100 ℃ of dryings after 10 hours, obtain C-LiFePO
4Product.
Embodiment 6
With 5mol Li
2CO
3, 10mol ferrous oxalate, 10mol (NH
4)
3PO
4, the carbon that obtains of 4000ml ethanol and the pyrolysis of 50g epoxy resin joins in the ball grinder, adds the diameter 10mm zirconia ball of milling simultaneously, ball milling is 8 hours under the 300r/min rotating speed, obtains uniform paste mixture material; Use 180 ℃ of spray dryings of centrifugal spray granulating and drying machine then, obtain presoma; Above-mentioned presoma is put into the atmosphere protection tube furnace, feed nitrogen,, be warmed up to 600 ℃ and constant temperature then 12 hours, naturally cool to room temperature in 450 ℃ of insulation 6h down; Above-mentioned material is joined micronizer pulverize, the gained crushed material is crossed 300 order reciprocating sieves in 100 ℃ of dryings after 10 hours, obtain C-LiFePO
4Product.
Embodiment 7
With 5mol Li
2CO
3, 9.8mol ferrous oxalate, 0.2mol MgO
2, 10mol (NH4)
3PO
4, the carbon that 4000ml ethanol and the pyrolysis of 50g epoxy resin obtain joins in the ball grinder, adds the diameter 8mm zirconia ball of milling simultaneously, and ball milling is 10 hours under the 350r/min rotating speed, obtains uniform paste mixture material; Use 200 ℃ of spray dryings of centrifugal spray granulating and drying machine then, obtain presoma; Above-mentioned presoma is put into the atmosphere protection tube furnace, feed nitrogen,, be warmed up to 650 ℃ and constant temperature then 12 hours, naturally cool to room temperature in 400 ℃ of insulation 10h down; Above-mentioned material is joined micronizer pulverize, the gained crushed material is crossed 300 order reciprocating sieves in 120 ℃ of dryings after 6 hours, obtain C-LiFe
0.98Mg
0.02PO
4Product.
Embodiment 8
With 4mol lithium carbonate, 2mol lithium acetate, 9.85mol four water acetic acid manganese, 0.15mol titanium oxide, 10mol (NH
4)
2HPO
4, 4000ml ethanol and 70g carbon nano-fiber join in the ball grinder, adds the diameter 8mm zirconia ball of milling simultaneously, ball milling is 10 hours under the 500r/min rotating speed, obtains uniform paste mixture material; Use 280 ℃ of spray dryings of centrifugal spray granulating and drying machine then, obtain presoma; Above-mentioned presoma is put into the atmosphere protection tube furnace, feed nitrogen,, be warmed up to 800 ℃ and constant temperature then 10 hours, naturally cool to room temperature in 475 ℃ of insulation 12h down; Above-mentioned material is joined micronizer pulverize, the gained crushed material is crossed 300 order reciprocating sieves in 120 ℃ of dryings after 8 hours, obtain C-LiMn
0.985Ti
0.015PO
4Product.
Embodiment 9
With 10mol lithium hydroxide, 10mol ferrous acetate, 10mol silicon dioxide, 3000ml deionized water and 160g acetylene black join in the ball grinder, add the diameter 10mm zirconia ball of milling simultaneously, ball milling is 6 hours under the 350r/min rotating speed, obtains uniform paste mixture material; Use 200 ℃ of spray dryings of centrifugal spray granulating and drying machine then, obtain presoma; Above-mentioned presoma is put into the atmosphere protection tube furnace, feed nitrogen and hydrogen (volume ratio 95: 5),, be warmed up to 750 ℃ and constant temperature then 18 hours, naturally cool to room temperature in 480 ℃ of insulation 12h down; Above-mentioned material is joined micronizer pulverize, the gained crushed material is crossed 300 order reciprocating sieves in 120 ℃ of dryings after 6 hours, obtain C-LiFeSiO
4Product.
Comparative example
With 10mol lithium hydroxide, 10mol ferrous acetate, 5mol Fe
2O
3, 3000ml deionized water and 210g acetylene black joins in the ball grinder, adds the diameter 8mm zirconia ball of milling simultaneously, ball milling is 8 hours under the 350r/min rotating speed, obtains uniform paste mixture material; Use the vacuum drier drying then, obtain presoma; Above-mentioned presoma is put into the atmosphere protection tube furnace, feed nitrogen and hydrogen,, be warmed up to 700 ℃ and constant temperature then 12 hours, naturally cool to room temperature in 450 ℃ of insulation 8h down; Above-mentioned material is joined micronizer pulverize, the gained crushed material is crossed 300 order reciprocating sieves in 100 ℃ of dryings after 8 hours, obtain C-LiFePO
4Product.
Performance test
C-Li with embodiment 1-9 and comparative example preparation
xM
1-yM '
y(XO
4)
nProduct, conductive black, polytetrafluoroethylene (PTFE) evenly mix in certain quality ratio (85: 10: 5), add an amount of n-formyl sarcolysine base pyrrolidones (NMP) ball milling then, be mixed and made into slurry, slurry is evenly coated on the aluminium foil (20 μ m), process high temperature (100 ℃) vacuum is (0.1MPa) behind the dry 4h, positive plate is made in roll-in, the about 2.0cm of electrode area
2, weightening finish 1-2mgcm
-2, be negative pole with the lithium sheet, electrolyte is 1mol/L LiPF
6/ EMC+DMC+EC (volume ratio 1: 1: 1), barrier film are the thick microporous polypropylene membrane of 0.025mm, are being full of high-purity Ar (relative humidity and O
2＜1%) dress up CR2025 type button simulated battery in the glove box, use the NEWARE battery test system that battery is carried out electric performance test, 0.2C discharges and recharges, and voltage range is 2.0-4.0V.
The material of embodiment 1-9 and comparative example preparation is become the 10Ah battery, carry out the multiplying power test.
The Winner2000 laser particle analyzer is analyzed sample.
SSA-3500 specific area tester is analyzed sample.
BT-300 powder tapping density instrument is analyzed sample.
The physics of the material of embodiment of the invention 1-9 and comparative example preparation and chemical property testing result see Table 1 and Figure of description Fig. 1～Fig. 5.
Table 1
By table 1 data as can be known, according to the material good conductivity that the inventive method makes, capacity height, good rate capability, even particle size distribution and easily control.
Material granule is even as can be seen by the SEM collection of illustrative plates of Fig. 1
The XRD diffracting spectrum existence at free from admixture peak as can be seen by Fig. 2.
As seen from Figure 3, it is better that the present invention adopts the material capacity performance of ferrous iron preparation.
As seen from Figure 4, the material cycle performance is fine.
By Fig. 5 and Fig. 6 as can be seen, adopt the material multiplying power of ferrous iron preparation to be better than adopting the material of ferric iron preparation.
The foregoing description just is used for description and interpretation content of the present invention, can not constitute limitation of the scope of the invention.Although the inventor has done in more detail the present invention and has enumerated, but, the content that those skilled in the art is disclosed according to summary of the invention part and embodiment can be made various modifications or/and additional or to adopt similar mode to substitute be obvious to described specific embodiment.
Claims (10)
1. the preparation method of an anode material of carbon-coated lithium ion battery is characterized in that, described preparation method comprises the steps: successively
1. Li compound, M compound, M ' compound, X compound and at least a inorganic conductive carbon are mixed, the gained mixture is done ball-milling treatment after adding solvent, the ball milling product obtains presoma through mist projection granulating, wherein, the mol ratio of Li in the described mixture: M: M ': X=0.95～1.05: 0.45～1.05: 0～0.55: 0.95～1.05, the inorganic conductive carbon content is 1～20wt%;
2. under the Buchholz protection atmosphere, presoma 200～500 ℃ of pre-burnings 2～10 hours, was then handled 2～24 hours at 500～800 ℃ of following double sinterings;
3. treat step 2. products therefrom do the material that pulverizing can obtain general molecular formula C-LixM1-yM ' y (XO4) n after being cooled to room temperature,
Wherein, 0＜x≤2,0≤y≤0.5,1≤n≤1.5, M is a transition metal, and M ' is selected among Mg, Ti, Cr, V or the Al at least a, and X is selected from S, P or Si.
2. preparation method as claimed in claim 1 is characterized in that, and is a kind of in M compound chosen from Fe, manganese, cobalt or the nickel salt of described step in 1..
3. preparation method as claimed in claim 2 is characterized in that described molysite refers to divalent iron salt, selects oxalic acid molysite or acetic acid molysite for use.
4. preparation method as claimed in claim 1 is characterized in that, the Li compound of described step in 1. is selected from lithium carbonate, lithium hydroxide, lithium dihydrogen phosphate, lithium acetate or the lithium nitrate at least a.
5. preparation method as claimed in claim 1, it is characterized in that the inorganic conductive carbon of described step in 1. is selected from behind native graphite, Delanium micro mist, carbon black granules, acetylene black particle, carbon nano-tube, carbon nano-fiber or the organic substance high temperature pyrolysis at least a in the resulting DIC.
6. preparation method as claimed in claim 1 is characterized in that, the solvent of described step in 1. is selected from least a in deionized water, ethanol, ethylene glycol, propyl alcohol, isopropyl alcohol, n-butanol, glycerine or the ethylenediamine.
7. preparation method as claimed in claim 1 is characterized in that, the gas of described step in 2. is at least a in hydrogen, nitrogen or the argon gas.
8. preparation method as claimed in claim 1 is characterized in that, the 2. middle pre-burning of described step is to handle 4～8 hours down at 300～500 ℃.
9. preparation method as claimed in claim 1 is characterized in that, the 2. middle double sintering of described step is to handle 5-20 hour down at 550～780 ℃.
10. preparation method as claimed in claim 1 is characterized in that, micronizer, airslide disintegrating mill, mechanical type pulverizer or compound pulverizer are adopted in the pulverizing of described step in 3..
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|---|---|---|---|
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| PCT/CN2009/001120 WO2011009231A1 (en) | 2009-07-20 | 2009-10-09 | Method for preparing carbon-coated positive material of lithium ion battery |
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