CN105047921A - Lithium ion battery cathode material composite lithium iron phosphate and preparation method thereof and lithium ion battery - Google Patents

Lithium ion battery cathode material composite lithium iron phosphate and preparation method thereof and lithium ion battery Download PDF

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Publication number
CN105047921A
CN105047921A CN201510409814.5A CN201510409814A CN105047921A CN 105047921 A CN105047921 A CN 105047921A CN 201510409814 A CN201510409814 A CN 201510409814A CN 105047921 A CN105047921 A CN 105047921A
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ion battery
lithium ion
iron phosphate
material composite
ball
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侯春平
马勇
王兴蔚
贺超
龚波林
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Ningxia Boulter Technology Co., Ltd.
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NINGXIA KOCEL NEW ENERGY MATERIAL Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a lithium ion battery cathode material composite lithium iron phosphate and a preparation method thereof and a lithium ion battery, and aims at reaching the technical effects that the capacity and the rate capability of the cathode material are improved and the cost is reduced. According to the lithium ion battery cathode material composite lithium iron phosphate disclosed by the invention, with lithium iron phosphate doped with a dopant as matrix, a TiC coating layer coats the outside of the matrix. The preparation method of the lithium ion battery cathode material composite lithium iron phosphate comprises the following steps: preparing TiC; preparing ball-milling slurry; and carrying out baking, ball-milling, pre-sintering, constant-temperature preservation, ball-milling or crushing and mechanical compaction treatment. According to the lithium ion battery disclosed by the invention, the lithium iron phosphate doped with the dopant is adopted by the cathode active material as the matrix; and the TiC coating layer coats the outside of the matrix. Compared with the prior art, by the electrical conductivity of the TiC, the capacity and the rate capacity of the lithium iron phosphate material are improved; the lithium ion battery cathode material is stable and good in corrosion resistance; polarization of the lithium ion battery is reduced; the electrode material is excellent in processability; and the preparation technology is simple, low in cost and suitable for industrial production.

Description

Lithium ion battery anode material composite lithium iron phosphate and preparation method thereof and lithium ion battery
Technical field
The present invention relates to a kind of cell positive material and preparation method thereof and adopt the battery, particularly a kind of LiFePO4 and preparation method thereof of this positive electrode and the lithium ion battery adopting LiFePO4.
Background technology
Along with the development of human society, energy crisis and environmental protection problem become increasingly conspicuous.Within 1991, first Sony company achieves the commercialization of lithium rechargeable battery, and this facilitates the development of electronics industry, information industry, auto industry, energy industry and environmental protection cause to a great extent.Lithium ion battery has been widely used in the mini-plants such as mobile communication equipment, portable computer, video camera, camera now, also the redundant electrical power of the electricity generation system such as solar energy, wind energy is become, the power supply of cordless power tool power supply and hybrid-electric car HEV, pure electric automobile EV.
The anode material for lithium-ion batteries that market has used mainly contains LiCoO 2, LiMn 2o 4, Ni-Co-Mn tertiary cathode material and LiFePO4, and former three occupies most market share, and LiFePO4 realizes industrialization, has been widely applied at electrokinetic cell, hybrid electric vehicle and pure electric vehicle at present, and output is also progressively increasing.Stratiform cobalt acid lithium hampers development and the application of power lithium-ion battery due to the shortcoming such as expensive, resource scarcity, poor stability always, and its range of application is also only limitted to compact battery.LiMn2O4 be follow cobalt acid lithium closely after the anode material for lithium-ion batteries that develops, pass through years of researches, material property is greatly improved, but its lower specific capacity, poor cycle performance make it apply and receive larger restriction, although by the improvement of recent years, cycle performance obtains certain improvement, but high temperature cyclic performance is not also solved preferably, limits its application in electrokinetic cell especially electric vehicle power sources.Tertiary cathode material had had large development in recent years, but this is only a compromise proposal, can not solve the cost of lithium ion battery, toxicity and safety issue at all.Analyze according to statistics, the demand of anode material for lithium-ion batteries will rapidly increase in recent years.
1997, Goodenough etc. at patent USA5,910, propose LiFePO in 382 4as the positive electrode of new type lithium ion battery, this material has that raw material sources are extensive, free from environmental pollution, security performance is good and the advantage such as theoretical capacity higher (170mAh/g), but there is the shortcoming that conductivity is low, high rate performance is poor simultaneously.M.Armand in 1999 etc. publish an article and claim carbon coated LiFePO 4 material performance of improving, thus have promoted the research application of LiFePO 4 material.The advantage that lithium iron phosphate positive material has is as follows: 1, fail safe is high, and LiFePO4 completely solves the security hidden trouble of cobalt acid lithium and LiMn2O4, can not constitute a threat to the life security of consumer.2, stability is high, and LiFePO4 voltage platform is stablized, and is 3.4VvsLi/Li +, the capacity stability of high-temperature charging is good, and storge quality is good.3, the long-life: the cycle life of ferric phosphate lithium cell reaches more than 2000 times.4, quickly-chargeable: ferric phosphate lithium cell 10C charges, and can be charged to the 80-90% of capacity for 6 minutes.5, environmental protection: use advantages of nontoxic raw materials, whole production process cleans nontoxic, unharmful substance discharges.6, low price, raw material sources are extensive, cheap, without strategic resource and scarce resource restriction.Therefore, the large-scale application of lithium iron phosphate positive material on power lithium-ion battery has been trend of the times.The output of LiFePO4 in 2014 breaks through ten thousand tons.
The preparation method of the LiFePO4 of prior art mainly contains solid phase method and liquid phase method, wherein, solid phase method comprises carbon thermal reduction (as application number 200410003477.1), Microwave synthesize (as application number 200610065211.9) and mechanical attrition method etc., and liquid phase method has sol-gal process (as application number 200410099216.4), hydro thermal method and coprecipitation (as application number 200410103485.3) etc.It is simple that solid phase method prepares LiFePO 4 material technique, and cost is low, be easy to realize industrialization, but have that capacity is lower, doubly forthright poor deficiency.Liquid phase method synthesizing iron lithium phosphate have capacity higher, doubly forthright good, material homogeneity is good, increase the less advantage of voltage drop with multiplying power, but also there is the shortcoming that preparation condition harshness, complex process, cost are high, be difficult to realize suitability for industrialized production.
Summary of the invention
The object of this invention is to provide a kind of lithium ion battery anode material composite lithium iron phosphate and preparation method thereof and lithium ion battery, the technical problem that solve improves positive electrode capacity and high rate performance, reduces costs.
The present invention is by the following technical solutions: a kind of lithium ion battery anode material composite lithium iron phosphate, and with the LiFePO4 doped with alloy for matrix, matrix is coated with TiC coating layer, and the quality of coating layer is 0.1 ~ 30% of substrate quality; Described alloy quality is 0.01 ~ 5.3% of LiFePO4 quality;
Described alloy is more than one in Zr, Zn, Ti, Mn, Sn, Al, Mg, Cu, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ag, Nb, lanthanum rich mischmetal Ml, cerium-rich mischmetal Mm, the oxide of aforementioned metal and salt;
Described oxide is ZrO 2, ZnO, TiO 2, MnO 2, SnO, Al 2o 3, MgO, CuO, Eu 2o 3, Gd 2o 3, Tb 4o 7, Dy 2o 3, Ho 2o 3, Er 2o 3, Tm 2o 3, Yb 2o 3, Lu 2o 3, Nb 2o 5, Ag 2o.La 2O 3、Nd 2O 3；
Described salt is Zr (SO 4) 24H 2o, Zn (CH 3cOO) 22H 2o, TiCl 36H 2o, Mn (CH 3cOO) 24H 2o, C 4h 6mnO 4(Mn (CH 3cOO) 2), SnCl 2, AlCl 3, MgCl 2, CuCl 2, EuCl 3, Gd 2(HPO 3) 3(H 2o) 2, TbF 3, Dy 3al 5o 12, C 4h 6o 4mg4H 2o.
A preparation method for lithium ion battery anode material composite lithium iron phosphate, comprises the following steps:
One, preparing TiC, is that Ti and the C powder of 98.5 ~ 99.9%, granularity < 1 μm is mixed to get mixture in the ratio 1:1 of amount of substance by purity; Under 100 ~ 400rpm rotating speed, wet ball grinding 2 ~ 20h, obtains slurry; After drying slurry, at 240 ~ 360MPa forming under the pressure, pressurize 3 ~ 5min, obtain green body cylinders, by base substrate with the programming rate of 2 ~ 20 DEG C/min, from room temperature to 1800 ~ 2400 DEG C, roasting 1 ~ 10h, after naturally cooling to room temperature, being crushed to granularity is nanoscale or submicron order, obtains TiC;
TiC is used for adding in step 2 or step 7, and carry out coated to the LiFePO4 of doping, the TiC quality added is 0.1 ~ 30% of alloy and LiFePO4 quality sum;
Two, by the lithium dihydrogen phosphate of purity >=99.9% and the source of iron of purity >=99.5%, in the ratio 0.90 ~ 1.20:1 of amount of substance, be mixed to get raw material, add the alloy of material quality 0.01 ~ 5.3%, rotating speed is 100 ~ 400rpm, wet ball grinding 2 ~ 36h, to nanoscale or submicron order, obtains ball milling slurry;
Described source of iron is ferrous oxalate, di-iron trioxide, ferrous acetate, ferric nitrate, iron hydroxide, tri-iron tetroxide, ferrous oxide or ferrous hydroxide;
Described alloy is more than one in Zr, Zn, Ti, Mn, Sn, Al, Mg, Cu, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ag, Nb, lanthanum rich mischmetal Ml, cerium-rich mischmetal Mm, the oxide of aforementioned metal and salt;
Described oxide is ZrO 2, ZnO, TiO 2, MnO 2, SnO, Al 2o 3, MgO, CuO, Eu 2o 3, Gd 2o 3, Tb 4o 7, Dy 2o 3, Ho 2o 3, Er 2o 3, Tm 2o 3, Yb 2o 3, Lu 2o 3, Nb 2o 5, Ag 2o, La 2o 3, Nd 2o 3;
Described salt is Zr (SO 4) 24H 2o, Zn (CH 3cOO) 22H 2o, TiCl 36H 2o, Mn (CH 3cOO) 24H 2o, C 4h 6mnO 4(Mn (CH 3cOO) 2), SnCl 2, AlCl 3, MgCl 2, CuCl 2, EuCl 3, Gd 2(HPO 3) 3(H 2o) 2, TbF 3, Dy 3al 5o 12, C 4h 6o 4mg4H 2o;
Three, ball milling slurry is dried;
Four, by dry thing ball milling 1 ~ 10h under 100 ~ 400rpm rotating speed, precursor is obtained;
Five, presoma is warmed up to 200 ~ 400 DEG C from room temperature with the programming rate of 2 ~ 5 DEG C, pre-burning 2 ~ 12h, is then warmed up to 500 ~ 800 DEG C with the programming rate of 2 ~ 5 DEG C, constant temperature 8 ~ 36h, naturally cools to room temperature;
Six, ball milling or pulverizing is 0.2 ~ 40 μm to granularity;
Seven, carry out mechanical jolt ramming process, obtain lithium ion battery anode material composite lithium iron phosphate.
Step one wet ball grinding of the present invention is 1:2 ~ 10 by the mass ratio of mixture and ball milling solvent, and the mass ratio of mixture and ball-milling medium is 1:3 ~ 5.
Step one green body cylinders diameter 20mm of the present invention, high 100mm.
Base substrate is 0.4 ~ 1m at flow by step one of the present invention 3/ h.M 3argon gas, carbon dioxide, heat up under helium or nitrogen protection, roasting.
Step 2 wet ball grinding of the present invention adds the dispersant of alloy and material quality sum 0.5 ~ 5 times, is 1:3 ~ 5 by the mass ratio of abrasive material and ball-milling medium.
Step 3 of the present invention is dried and is adopted stirring and drying, spraying dry or flash distillation, and the dry matter amount water content obtained is less than 1%.
Presoma is 0.4 ~ 1m at flow by step 5 of the present invention 3/ h.M 3non-oxidizing gas CO, CO 2, He, Ar or N 2under atmosphere protection, pre-burning, constant temperature.
Step 6 ball milling of the present invention ball milling 1 ~ 10h under 100 ~ 400rpm rotating speed.
A kind of lithium ion battery of lithium ion battery anode material composite lithium iron phosphate, be provided with positive pole, described positive electrode active materials is with the LiFePO4 doped with alloy for matrix, and matrix is coated with TiC coating layer, and the quality of coating layer is 0.1 ~ 30% of substrate quality; Described alloy quality is 0.01 ~ 5% of LiFePO4 quality;
Described alloy is more than one in Zr, Zn, Ti, Mn, Sn, Al, Mg, Cu, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ag, Nb, lanthanum rich mischmetal Ml, cerium-rich mischmetal Mm, the oxide of aforementioned metal and salt;
Described oxide is ZrO 2, ZnO, TiO 2, MnO 2, SnO, Al 2o 3, MgO, CuO, Eu 2o 3, Gd 2o 3, Tb 4o 7, Dy 2o 3, Ho 2o 3, Er 2o 3, Tm 2o 3, Yb 2o 3, Lu 2o 3, Nb 2o 5, Ag 2o.La 2O 3、Nd 2O 3；
Described salt is Zr (SO 4) 24H 2o, Zn (CH 3cOO) 22H 2o, TiCl 36H 2o, Mn (CH 3cOO) 24H 2o, C 4h 6mnO 4(Mn (CH 3cOO) 2), SnCl 2, AlCl 3, MgCl 2, CuCl 2, EuCl 3, Gd 2(HPO 3) 3(H 2o) 2, TbF 3, Dy 3al 5o 12, C 4h 6o 4mg4H 2o.
The present invention compared with prior art, utilizes the conductivity of TiC, improves LiFePO 4 material capacity and doubly forthright, stablize and good corrosion resistance, lithium ion battery polarization reduces, and electrode material processing characteristics is excellent, preparation technology is simple, with low cost, is suitable for suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the XRD collection of illustrative plates of the lithium ion battery anode material composite lithium iron phosphate of embodiment 1.
Fig. 2 is the stereoscan photograph of lithium ion battery anode material composite lithium iron phosphate under 2000 times of embodiment 1.
Fig. 3 is the charging and discharging curve figure of lithium ion battery anode material composite lithium iron phosphate under 2.5-3.9V, 0.12C multiplying power of embodiment 1.
Fig. 4 is the charging and discharging curve figure of lithium ion battery anode material composite lithium iron phosphate under 2.5-3.9V, 1.2C multiplying power of embodiment 1.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail.
Lithium ion battery anode material composite lithium iron phosphate of the present invention, doped with alloy in LiFePO4, alloy quality is 0.01 ~ 5% of LiFePO4 quality.With the LiFePO4 doped with alloy for matrix, matrix is coated with TiC coating layer, and the quality of coating layer is 0.1 ~ 30% of substrate quality.
Alloy is more than one in Zr, Zn, Ti, Mn, Sn, Al, Mg, Cu, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ag, Nb, lanthanum rich mischmetal Ml, cerium-rich mischmetal Mm, the oxide of aforementioned metal and salt.
Oxide is ZrO 2, ZnO, TiO 2, MnO 2, SnO, Al 2o 3, MgO, CuO, Eu 2o 3, Gd 2o 3, Tb 4o 7, Dy 2o 3, Ho 2o 3, Er 2o 3, Tm 2o 3, Yb 2o 3, Lu 2o 3, Nb 2o 5, Ag 2o.La 2O 3、Nd 2O 3。
Salt is Zr (SO 4) 24H 2o, Zn (CH 3cOO) 22H 2o, TiCl 36H 2o, Mn (CH 3cOO) 24H 2o, C 4h 6mnO 4(Mn (CH 3cOO) 2), SnCl 2, AlCl 3, MgCl 2, CuCl 2, EuCl 3, Gd 2(HPO 3) 3(H 2o) 2, TbF 3, Dy 3al 5o 12, C 4h 6o 4mg4H 2o.
Lithium ion battery anode material composite lithium iron phosphate of the present invention, granularity is 0.2 ~ 40 μm, and specific area is 0.5 ~ 50m 2/ g, for irregularly shaped.
The preparation method of lithium ion battery anode material composite lithium iron phosphate of the present invention, comprises the following steps:
One, preparing TiC, is that Ti and the C powder of 98.5 ~ 99.9%, granularity < 1 μm is mixed to get mixture in the ratio 1:1 of amount of substance by purity;
Be 1:2 ~ 10 by the mass ratio of mixture and ball milling solvent, the mass ratio of mixture and ball-milling medium is 1:3 ~ 5, and under 100 ~ 400rpm rotating speed, wet ball grinding 2 ~ 20h, obtains slurry;
Dry after slurry, loaded in stainless steel mould, under 240 ~ 360MPa pressure, isostatic compaction, pressurize 3 ~ 5min, obtains the green body cylinders of diameter 20mm, high 100mm, then is 0.4 ~ 1m by base substrate at flow 3/ h.M 3argon gas, carbon dioxide, under helium or nitrogen protection, with the programming rate of 2 ~ 20 DEG C/min from room temperature to 1800 ~ 2400 DEG C, roasting 1 ~ 10h, after naturally cooling to room temperature, being crushed to granularity by prior art is nanoscale or submicron order, obtains TiC.
Ball milling solvent is the mixture of pure water, ethanol, acetone, ethanol and water or the mixture of ethanol and acetone.
Dry slurry and adopt stirring and drying, spraying dry or flash evaporation drying, the quality of material water content after oven dry is less than 1%.Stirring and drying, at rotating speed 100 ~ 400rpm, naturally cools to room temperature after drying under the condition that temperature is 200 ~ 350 DEG C.Spraying dry inlet temperature 220 DEG C, outlet temperature 120 DEG C.The inlet temperature of flash evaporation drying is: 200 ~ 350 DEG C.
Wet ball grinding adopts planetary ball mill, horizontal drum ball mill or stirring ball mill, and ball-milling medium is the stainless steel of Φ 5mm, corundum, zirconia or agate.
Pulverize and adopt planetary ball mill, horizontal ball mill, tumbling ball mill, airslide disintegrating mill or mechanical crusher.
In the method for the invention, gas flow unit m 3/ h.M 3represent at unit volume M 3in, the volume flow m that h per hour flows through 3.Be applicable to the different roasting of structure or heating furnace, as tube furnace, box type furnace, rotary furnace or tunnel cave.
TiC is used for adding in step 2 or step 7, and carry out coated to the LiFePO4 of doping, the TiC quality added is 0.1 ~ 30% of alloy and LiFePO4 quality sum.
TiC has good conductivity, and conductivity is 1.90 × 10 4s/cm, and chemical property is more stable, good corrosion resistance.The electric conductivity of TiC is far above the conductivity (about 100S/cm) of conductive agent carbon black conventional at present.It is coated that the present invention utilizes electric conducting material TiC to carry out doping to lithium ion battery material LiFePO4, the electric conductivity of LiFePO 4 material is made to obtain remarkable improvement, its discharge capacity and high rate performance have also been obtained raising, material polarization reduces, 0.12C first discharge capacity is 156.2mAh/g, first efficiency be 96.3%, 1.2C first discharge capacity be 132.5mAh/g, efficiency is 88.2% first.
Two, by the lithium dihydrogen phosphate of purity >=99.9% and the source of iron of purity >=99.5%, in the ratio 0.90 ~ 1.20:1 of amount of substance, be mixed to get raw material, add the alloy of material quality 0.01 ~ 5.3%, add the dispersant of alloy and material quality sum 0.5 ~ 5 times, be 1:3 ~ 5 by the mass ratio of abrasive material and ball-milling medium, rotating speed is 100 ~ 400rpm, ball milling 2 ~ 36h, to nanoscale or submicron order, obtains ball milling slurry.
If add TiC in step 2, add the TiC of alloy and material quality sum 0.1 ~ 30%, in-stiu coating is carried out to the LiFePO4 of doping, is milled to nanoscale or submicron order, obtains ball milling slurry.
Source of iron is ferrous oxalate, di-iron trioxide (iron oxide), ferrous acetate, ferric nitrate, iron hydroxide, tri-iron tetroxide, ferrous oxide or ferrous hydroxide.
Alloy is more than one in Zr, Zn, Ti, Mn, Sn, Al, Mg, Cu, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ag, Nb, lanthanum rich mischmetal Ml, cerium-rich mischmetal Mm, the oxide of aforementioned metal and salt.
Oxide is ZrO 2, ZnO, TiO 2, MnO 2, SnO, Al 2o 3, MgO, CuO, Eu 2o 3, Gd 2o 3, Tb 4o 7, Dy 2o 3, Ho 2o 3, Er 2o 3, Tm 2o 3, Yb 2o 3, Lu 2o 3, Nb 2o 5, Ag 2o, La 2o 3, Nd 2o 3.
Salt is Zr (SO 4) 24H 2o, Zn (CH 3cOO) 22H 2o, TiCl 36H 2o, Mn (CH 3cOO) 24H 2o, C 4h 6mnO 4(Mn (CH 3cOO) 2), SnCl 2, AlCl 3, MgCl 2, CuCl 2, EuCl 3, Gd 2(HPO 3) 3(H 2o) 2, TbF 3, Dy 3al 5o 12, C 4h 6o 4mg4H 2o.
Dispersant is pure water and/or ethanol.
Ball milling adopts planetary ball mill, horizontal drum ball mill or stirring ball mill, and ball-milling medium is the stainless steel of Φ 5mm, corundum, zirconia or agate.
This step improves the ion diffusivity of material by bulk phase-doped alloy.The coating layer of the particle surface that in-stiu coating is formed is even, and can to improve between material granule and and collector between contact and conductivity, make conductivity be increased to 1.9 × 10 4s/cm.The size of LiFePO4 crystal grain can be reduced in addition, shorten Li +diffusion admittance, improves the microstructure of material granule, improves specific surface area active, improves the chemical property of material.
Three, by the oven dry of ball milling slurry agitation, spraying dry or flash distillation, obtain dry thing, dry matter amount water content is less than 1%.
Stirring and drying is 100 ~ 400rpm at rotating speed, and temperature is naturally cool to room temperature after drying under the condition of 200 ~ 350 DEG C.Spraying dry inlet temperature 220 DEG C, outlet temperature 120 DEG C.The inlet temperature of flash evaporation drying is 200 ~ 350 DEG C.
Four, by dry thing ball milling 1 ~ 10h under 100 ~ 400rpm rotating speed, precursor is obtained.
Ball milling adopts planetary ball mill, horizontal drum ball mill or stirring ball mill, and ball-milling medium is the stainless steel of Φ 5mm, corundum, zirconia or agate.The mass ratio of dry thing and ball-milling medium is 1:3 ~ 5.
Five, be 0.4 ~ 1m by presoma at flow 3/ h.M 3non-oxidizing gas CO, CO 2, He, Ar or N 2under atmosphere protection, in tube furnace, box type furnace, rotary furnace or tunnel cave, be warmed up to 200 ~ 400 DEG C from room temperature with the programming rate of 2 ~ 5 DEG C; pre-burning 2 ~ 12h; then be warmed up to 500 ~ 800 DEG C with the programming rate of 2 ~ 5 DEG C, constant temperature 8 ~ 36h, naturally cools to room temperature.
The stability of LiFePO 4 material mainly comes from the olivine structural of ordering, therefore preparation process in, the growth of the olivine structural of ordering and the control of impurity very important.In addition, because ferro element is very easy to from Fe in the process of preparation 2+be oxidized to Fe 3+, and then generate the LiFePO of non-pure phase 4, make LiFePO 4quality and chemical property be affected.Therefore at non-oxidizing gas CO, CO 2, He, Ar or N 2under atmosphere protection, first pre-burning is the LiFePO4 that obtains of Isothermal sinter again, ensure that the growth of the olivine structural of ordering, to the control of impurity and the change of ferro element chemical state, guarantees to prepare pure phase LiFePO4.
Six, ball milling 1 ~ 10h under 100 ~ 400rpm rotating speed, or pulverize, be 0.2 ~ 40 μm to granularity.
Ball milling adopts planetary ball mill, horizontal drum ball mill or tumbling ball mill, and ball-milling medium is the stainless steel of Φ 5mm, corundum, zirconia or agate.
Pulverize and adopt airslide disintegrating mill or mechanical crusher.
Seven, carry out mechanical jolt ramming process, obtain lithium ion battery anode material composite lithium iron phosphate.
If add TiC in step 7, first add the TiC of the LiFePO4 quality 0.1 ~ 30% after doping, then carry out mechanical jolt ramming process, carry out coated to the LiFePO4 quality after doping, obtain lithium ion battery anode material composite lithium iron phosphate.
Machinery jolt ramming process adopts plain bumper, VC mixer, merges machine or kneader.
The tap density of the LiFePO4 after doping is little, and volume and capacity ratio is more much lower than the sour lithium of cobalt, and the battery electrode volume made is large, have impact on its practical application.By mechanical jolt ramming process, namely by mechanical presses, make material repeatedly mix dispersion under the effect of equipment shearing force, discharge air.The bulky grain of material can be carried out fragmentation simultaneously, not only make its granule size distribute more even, further improve drawing abillity.The tap density of the material obtained is 1.35 ~ 1.55g/cm 3.
The lithium ion battery anode material composite lithium iron phosphate that embodiment prepares, the KYKY2800B type ESEM of Chinese science Instrument Ltd. is adopted to carry out Analysis of Surface Topography to it, its microscopic appearance is irregularly shaped, and particle surface can see obvious coating layer, this layer of coating layer contributes to stoping growing up of particle when LiFePO4 is formed, and also reaches the effect improving conductivity.Recording granularity with the Mastersizer2000 laser particle analyzer of Malvern Instr Ltd. of Britain is 0.2 ~ 40 μm, and recording specific area with the specific-surface area detection instrument of Kang Ta instrument company of the U.S. is 0.5 ~ 50m 2/ g, recording tap density with the BT-301 tap density tester of Chinese Dandong Bai Te Instrument Ltd. is 1.35 ~ 1.55g/cm 3.
Lithium ion battery anode material composite lithium iron phosphate embodiment prepared is as positive electrode active materials, by positive electrode active materials: conductive agent carbon black SUPER-P: binding agent Kynoar PVDF mass ratio 90:5:5, with 1-METHYLPYRROLIDONE NMP do solvent evenly after be applied on Al paper tinsel, after 110 DEG C of dry 10h, spreading punching obtains positive pole, take metal lithium sheet as negative pole, barrier film adopts Celgard2400, and electrolyte is 1molL -1liPF 6/ DMC+DEC+EC, volume ratio is 1:1:1, assembles in the Braun MBRAUN glove box of argon shield, obtains the CR2025 fastening lithium ionic cell tested.Adopt Wuhan Land Electronic Co., Ltd. CT2001A battery testing system, respectively with the charging and discharging currents density discharge and recharge of 0.12C and 1.2C, charging/discharging voltage is the chemical property of 2.5-3.9V, test simulation battery.
Capacity and the high rate performance of the lithium ion battery of the lithium iron phosphate positive material of the TiC of being coated with conductive agent of the present invention are obtained for significant lifting, and battery polarization reduces, materials processing excellent performance.Material 0.12C first discharge capacity is 156.2mAh/g, first efficiency be 96.3%, 1.2C first discharge capacity be 132.5mAh/g, efficiency is 88.2% first.
Embodiment 1
Purity is that Ti and the C powder of 98.5%, granularity < 1 μm mixes in amount of substance ratio 1:1 by one, TiC preparation, in planetary ball mill, be 1:2 by the mass ratio of mixture and pure water, it is 1:3 that mixture and stainless steel grind the mass ratio be situated between, with 400rpm rotating speed ball milling 2h, 300 DEG C of flash evaporation dryings, under 240MPa pressure, isostatic compaction, pressurize 5min, obtaining the green body cylinders of diameter 20mm, high 100mm, is 0.4m at flow 3/ h.M 3under nitrogen protection, with the programming rate of 2 DEG C/min from room temperature to 1800 DEG C of roasting 10h, after naturally cooling to room temperature, be crushed to nanoscale or submicron order with airslide disintegrating mill, obtain TiC stand-by.
Two, lithium dihydrogen phosphate 120.8g, iron oxide 90.3g, magnesium acetate 0.0105g, manganese acetate 0.0073g, niobium pentaoxide 0.0016g, silver oxide 0.0017g is taken, alloy is 0.01% of material quality, add in the ethanol of alloy and material quality sum 0.5 times while stirring, be 1:3 by the mass ratio of abrasive material and ball-milling medium, planetary ball mill ball milling 10h under 200rpm rotating speed is used to nanoscale or submicron order, to obtain ball milling slurry.Ball-milling medium is the stainless steel ball of Φ 5mm, in this step, adds TiC simultaneously, and carry out coated to the LiFePO4 of doping, the TiC quality added is 0.1% of alloy and material quality sum.
Three, ball milling slurry is 100rpm at rotating speed, and temperature is naturally cool to room temperature after drying under the condition of 280 DEG C, obtains dry thing.
Four, be that ball-milling medium ball milling 10h under 100rpm rotating speed obtains precursor with zirconia ball by dry thing planetary ball mill.
Five, presoma is 0.4m at flow 3/ h.M 3nitrogen protection under in tube furnace, be warmed up to 300 DEG C from room temperature with the programming rate of 2 DEG C, pre-burning 6h, be then warmed up to 700 DEG C with the programming rate of 2 DEG C, constant temperature 10h, naturally cools to room temperature.
Six, with planetary ball mill ball milling 3h under 200rpm rotating speed, it is 0.2 ~ 40 μm to granularity.
Seven, carry out jolt ramming process with plain bumper, obtain lithium ion battery anode material composite lithium iron phosphate.
After the lithium ion battery anode material composite lithium iron phosphate (material) that embodiment 1 obtains crosses 200 mesh sieves, do XRD test, scanning electron microscope analysis, quantitative measurement and electrochemical property test.As shown in Figure 1, the material X-ray diffraction peak prepared is consistent with the standard feature peak of LiFePO4, all has regular olivine-type structure, does not occur dephasign diffraction maximum.And peak type is narrow and sharp-pointed, and diffraction peak intensity is high, illustrates that the LiFePO4 degree of crystallinity of coated preparation is higher.As shown in Figure 2, the microscopic appearance of material is irregularly shaped, and particle surface can see obvious coating layer.Material particle size is d50=18.8 μm, and specific area is 25.134m 2/ g, tap density is 1.47g/cm 3.The chemical property of test simulation battery, respectively with the charging and discharging currents density discharge and recharge of 0.12C and 1.2C, charging/discharging voltage is 2.5-3.9V, and when 3.9V, constant voltage is charged to cut-off current is 0.01mA and 0.03mA.As shown in Figure 3, the 0.12C of material first discharge capacity is 156.2mAh/g, and efficiency is 96.3% first, and as shown in Figure 4, the 1.2C of material first discharge capacity is 132.5mAh/g, and efficiency is 88.2% first.
Embodiment 2
One, TiC preparation, be 98.5% by purity, Ti and the C powder of granularity < 1 μm mixes in amount of substance ratio 1:1, in horizontal drum ball mill, be 1:4 by the mass ratio of mixture and ethanol, it is 1:3 that mixture and stainless steel grind the mass ratio be situated between, with 300rpm rotating speed ball milling 10h, inlet temperature 220 DEG C, spraying dry under outlet temperature 120 DEG C of conditions, under 260MPa pressure, isostatic compaction, pressurize 5min is pressed into the green body cylinders of diameter 20mm, high 100mm, is 0.4m at flow 3/ h.M 3under nitrogen atmosphere protection, with the programming rate of 5 DEG C/min from room temperature to 2000 DEG C of roasting 8h, after naturally cooling to room temperature, be crushed to nanoscale or submicron order with planetary ball mill, obtain TiC stand-by.
Two, lithium dihydrogen phosphate 125g, ferrous oxalate 180.1g, magnesium oxide 3.2g, aluminium oxide 3.05g, cupric oxide 1.35g, lanthana 0.4g is taken, alloy is 2.62% of material quality, add in the pure water of alloy and material quality sum 5 times while stirring, be 1:3 by the mass ratio of abrasive material and ball-milling medium, planetary ball mill ball milling 36h under 100rpm rotating speed is used to nanoscale or submicron order, to obtain ball milling slurry.Ball-milling medium is the stainless steel ball of Φ 5mm.
Three, ball milling slurry is spraying dry inlet temperature 220 DEG C, outlet temperature 120 DEG C.After naturally cool to room temperature, obtain dry thing.
Four, be that ball-milling medium ball milling 10h under 100rpm rotating speed obtains precursor with zirconia ball by dry thing horizontal drum ball mill.
Five, presoma is 0.6m at flow 3/ h.M 3nitrogen protection under in box type furnace, be warmed up to 200 DEG C from room temperature with the programming rate of 3 DEG C, pre-burning 12h, be then warmed up to 500 DEG C with the programming rate of 3 DEG C, constant temperature 36h, naturally cools to room temperature.
Six, with planetary ball mill ball milling 10h under 100rpm rotating speed, it is 0.2 ~ 40 μm to granularity.
Seven, add the TiC that quality is alloy and material quality sum 1%, carry out mechanical jolt ramming process with plain bumper, obtain lithium ion battery anode material composite lithium iron phosphate.
The material particle size d50=38.9 μm that embodiment 2 is obtained, specific area is 48.32m 2/ g, tap density is 1.49g/cm 3.Recording the material 0.12C capacity first that discharges is 154.86mAh/g, and efficiency is 97.3%, the 1.2C capacity first that discharges first is 135.1mAh/g, and efficiency is 89.5% first.
Embodiment 3
One, TiC preparation, be 99.0% by purity, Ti and the C powder of granularity < 1 μm mixes in amount of substance ratio 1:1, in stirring ball mill, be 1:5 by the mass ratio of mixture and acetone, it is 1:4 that mixture and corundum grind the mass ratio be situated between, with 300rpm rotating speed ball milling 10h, be 400rpm at rotating speed, temperature is naturally cool to room temperature, under 280MPa pressure after drying under the condition of 350 DEG C, isostatic compaction, pressurize 4min, is pressed into the green body cylinders of diameter 20mm, high 100mm, is 0.6m at flow 3/ h.M 3under carbon dioxide atmosphere protection, with the programming rate of 5 DEG C/min from room temperature to 2000 DEG C of roasting 8h, after naturally cooling to room temperature, be crushed to nanoscale or submicron order with horizontal ball mill, obtain TiC stand-by.
Two, lithium dihydrogen phosphate 125g, tri-iron tetroxide 91.5g, magnesium oxide 4.12g, niobium pentaoxide 0.85g, silver oxide 1.25g, manganese acetate 5.3g is taken, alloy is 5.32% of material quality, add the TiC that quality is alloy and material quality sum 5% simultaneously, in the pure water adding alloy and material quality sum 3 times while stirring and ethanol mixed dispersant (volume ratio 50:50), be 1:4 by the mass ratio of abrasive material and ball-milling medium, planetary ball mill ball milling 20h under 200rpm rotating speed is used to nanoscale or submicron order, to obtain ball milling slurry.Ball-milling medium is the agate of Φ 5mm.
Three, ball milling slurry is 200rpm at rotating speed, and temperature is naturally cool to room temperature after drying under the condition of 210 DEG C, obtains dry thing.
Four, be that ball-milling medium ball milling 6h under 200rpm rotating speed obtains precursor with zirconia by dry thing planetary ball mill.
Five, presoma is 0.6m at flow 3/ h.M 3argon shield under in rotary furnace, be warmed up to 400 DEG C from room temperature with the programming rate of 4 DEG C, pre-burning 2h, be then warmed up to 800 DEG C with the programming rate of 4 DEG C, constant temperature 8h, naturally cools to room temperature.
Six, with planetary ball mill ball milling 1h under 400rpm rotating speed, it is 0.2 ~ 40 μm to granularity.
Seven, carry out jolt ramming process with plain bumper, obtain lithium ion battery anode material composite lithium iron phosphate.
The material granularity d50=0.53 μm that embodiment 3 is obtained, specific area is 2.520m 2/ g, tap density is 1.54g/cm 3.Recording the material 0.12C capacity first that discharges is 157.0mAh/g, and efficiency is 97.8%, the 1.2C capacity first that discharges first is 130.4mAh/g, and efficiency is 89.4% first.
Embodiment 4
One, TiC preparation, be 99.5% by purity, Ti and the C powder of granularity < 1 μm mixes in amount of substance ratio 1:1, in planetary ball mill, be 1:6 by the mass ratio of the mixture of mixture and ethanol and pure water, it is 1:4 that mixture and zirconia grind the mass ratio be situated between, with 200rpm rotating speed ball milling 15h, flash evaporation drying under inlet temperature is 350 DEG C of conditions, under 300MPa pressure, isostatic compaction, pressurize 4min, being pressed into the green body cylinders of diameter 20mm, high 100mm, is 0.8m at flow 3/ h.M 3under carbon dioxide atmosphere protection, with the programming rate of 10 DEG C/min from room temperature to 2200 DEG C of roasting 5h, after naturally cooling to room temperature, be crushed to nanoscale or submicron order with tumbling ball mill, obtain TiC stand-by.
Two, lithium dihydrogen phosphate 125g, ferrous oxalate 188g, magnesium oxide 4.8g, aluminium oxide 3.2g, cupric oxide 1.58g, neodymia 0.58g is taken, alloy is 3.25% of material quality, add in the pure water of alloy and material quality sum 4 times while stirring, be 1:4 by the mass ratio of abrasive material and ball-milling medium, planetary ball mill ball milling 10h under 300rpm rotating speed is used to nanoscale or submicron order, to obtain ball milling slurry.Ball-milling medium is the corundum of Φ 5mm.
Three, ball milling slurry spraying dry, inlet temperature 220 DEG C, outlet temperature 120 DEG C, naturally cools to room temperature, obtains dry thing.
Four, by dry thing horizontal drum ball mill with corundum ball for ball-milling medium ball milling 4h under 300rpm rotating speed obtains precursor.
Five, presoma is 0.8m at flow 3/ h.M 3carbon-dioxide protecting under in tunnel cave, be warmed up to 300 DEG C from room temperature with the programming rate of 5 DEG C, pre-burning 9h, be then warmed up to 600 DEG C with the programming rate of 5 DEG C, constant temperature 15h, naturally cools to room temperature.
Six, with horizontal drum ball mill ball milling 10h under 100rpm rotating speed, it is 0.2 ~ 40 μm to granularity.
Seven, add the TiC that quality is alloy and material quality sum 10%, carry out jolt ramming process with plain bumper, obtain lithium ion battery anode material composite lithium iron phosphate.
The material particle size d50=4.14 μm that embodiment 4 is obtained, specific area is 34.32m 2/ g, tap density is 1.39g/cm 3.Recording the material 0.12C capacity first that discharges is 158.35mAh/g, and efficiency is 97.9%, the 1.2C capacity first that discharges first is 132.4mAh/g, and efficiency is 90.4% first.
Embodiment 5
One, TiC preparation, be 99.9% by purity, Ti and the C powder of granularity < 1 μm mixes in amount of substance ratio 1:1, in horizontal drum ball mill, be 1:8 by the mass ratio of the mixture of mixture and ethanol and acetone, it is 1:5 that mixture and agate grind the mass ratio be situated between, with 100rpm rotating speed ball milling 20h, inlet temperature 220 DEG C, under outlet temperature 120 DEG C of conditions, spraying dry is dried, under 320MPa pressure, isostatic compaction, pressurize 3min, is pressed into the green body cylinders of diameter 20mm, high 100mm, is 1m at flow 3/ h.M 3under argon gas atmosphere protection, with the programming rate of 10 DEG C/min from room temperature to 2200 DEG C of roasting 5h, after naturally cooling to room temperature, be crushed to nanoscale or submicron order with mechanical crusher, obtain TiC stand-by.
Two, lithium dihydrogen phosphate 124g, iron hydroxide 89.0g, magnesium oxide 4.1g, niobium pentaoxide 1.3g, cupric oxide 1.1g, manganese acetate 3.2g is taken, alloy is 4.55% of material quality, add the TiC that quality is alloy and material quality sum 20% simultaneously, in the pure water adding alloy and material quality sum 2 times while stirring and ethanol mixed dispersant (volume ratio 50:50), be 1:5 by the mass ratio of abrasive material and ball-milling medium, planetary ball mill ball milling 5h under 400rpm rotating speed is used to nanoscale or submicron order, to obtain ball milling slurry.Ball-milling medium is the corundum of Φ 5mm.
Three, ball milling slurry is 400rpm at rotating speed, and temperature is naturally cool to room temperature after drying under the condition of 200 DEG C, obtains dry thing.
Four, be that ball-milling medium ball milling 1h under 400rpm rotating speed obtains precursor with stainless steel ball by dry thing planetary ball mill.
Five, presoma is 0.6m at flow 3/ h.M 3argon shield under in box type furnace, be warmed up to 360 DEG C from room temperature with the programming rate of 5 DEG C, pre-burning 2.5h, be then warmed up to 750 DEG C with the programming rate of 5 DEG C, constant temperature 10h, naturally cools to room temperature.
Six, being crushed to granularity with airslide disintegrating mill is 0.2 ~ 40 μm.
Seven, carry out jolt ramming process with plain bumper, obtain lithium ion battery anode material composite lithium iron phosphate.
The material particle size d50=6.86 μm that embodiment 5 is obtained, specific area is 15.632m 2/ g, tap density is 1.49g/cm 3.Recording the material 0.12C capacity first that discharges is 158.2mAh/g, and efficiency is 98.1%, the 1.2C capacity first that discharges first is 133.5mAh/g, and efficiency is 89.2% first.
Embodiment 6
Purity is that Ti and the C powder of 99.9%, granularity < 1 μm mixes in amount of substance ratio 1:1 by one, TiC preparation, in stirring ball mill, be 1:10 by the mass ratio of mixture and pure water, it is 1:5 that mixture and agate grind the mass ratio be situated between, with 100rpm rotating speed ball milling 20h, flash evaporation drying under inlet temperature is 200 DEG C of conditions, under 360MPa pressure, isostatic compaction, pressurize 3min, being pressed into the green body cylinders of diameter 20mm, high 100mm, is 1m at flow 3/ h.M 3under helium atmosphere protection, with the programming rate of 20 DEG C/min from room temperature to 2400 DEG C of roasting 1h, after naturally cooling to room temperature, be crushed to nanoscale or submicron order with mechanical crusher, obtain TiC stand-by.
Two, lithium dihydrogen phosphate 125g, iron oxide 92g, magnesium acetate 5.8g, manganese acetate 2.5g, niobium pentaoxide 1.12g is taken, alloy is 4.34% of material quality, add in the ethanol of alloy and material quality sum 1 times while stirring, be 1:5 by the mass ratio of abrasive material and ball-milling medium, planetary ball mill ball milling 2h under 400rpm rotating speed is used to nanoscale or submicron order, to obtain ball milling slurry.Ball-milling medium is the agate of Φ 5mm.
Three, ball milling slurry is 300rpm at rotating speed, and temperature is naturally cool to room temperature after drying under the condition of 280 DEG C, obtains dry thing.
Four, be that ball-milling medium ball milling 1h under 400rpm rotating speed obtains precursor with zirconia ball by dry thing planetary ball mill.
Five, presoma is 1m at flow 3/ h.M 3nitrogen protection under in box type furnace, be warmed up to 270 DEG C from room temperature with the programming rate of 5 DEG C, pre-burning 6h, be then warmed up to 750 DEG C with the programming rate of 5 DEG C, constant temperature 14h, naturally cools to room temperature.
Six, being crushed to granularity with mechanical crusher is 0.2 ~ 40 μm.
Seven, add the TiC that quality is alloy and material quality sum 30%, carry out jolt ramming process with plain bumper, obtain lithium ion battery anode material composite lithium iron phosphate.
The material particle size d50=8.25 μm that embodiment 6 is obtained, specific area is 16.430m 2/ g, tap density is 1.51g/cm 3.Recording the material 0.12C capacity first that discharges is 158.6mAh/g, and efficiency is 98.1%, the 1.2C capacity first that discharges first is 132.2mAh/g, and efficiency is 89.4% first.
In embodiment 1-6, source of iron only lists ferrous oxalate, di-iron trioxide, iron hydroxide and tri-iron tetroxide, and alloy only lists Al 2o 3, MgO, CuO, Nb 2o 5, Ag 2o, La 2o 3, Nd 2o 3, C 4h 6mnO 4(Mn (CH 3cOO) 2) and C 4h 6o 4mg4H 2o.In all sources of iron listed in the present invention and alloy, be not enumerated in embodiment, all can synthesize with corresponding lithium source the LiFePO4 generating metal ion mixing, in formation material of the present invention, role is for providing ferro element and metal-doped ion, material is played stably structure and improve the effect of conductivity, so the source of iron be not enumerated in embodiment and alloy are suitable for the present invention in charge and discharge process.
The present invention utilizes the conductivity of TiC, improves LiFePO 4 material capacity and doubly forthright, stable and good corrosion resistance, and lithium ion battery polarization reduces, and electrode material processing characteristics is excellent, and preparation technology is simple, with low cost, is applicable to suitability for industrialized production.The solid phase method effectively improving prior art prepares LiFePO4, capacity is lower, doubly forthright poor deficiency, also overcome prior art simultaneously and adopt liquid phase method synthesizing iron lithium phosphate, preparation condition harshness, complex process, cost be high, be difficult to the deficiency realizing suitability for industrialized production.

Claims (10)

1. a lithium ion battery anode material composite lithium iron phosphate, it is characterized in that: described lithium ion battery anode material composite lithium iron phosphate with the LiFePO4 doped with alloy for matrix, matrix is coated with TiC coating layer, and the quality of coating layer is 0.1 ~ 30% of substrate quality; Described alloy quality is 0.01 ~ 5.3% of LiFePO4 quality;
Described alloy is more than one in Zr, Zn, Ti, Mn, Sn, Al, Mg, Cu, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ag, Nb, lanthanum rich mischmetal Ml, cerium-rich mischmetal Mm, the oxide of aforementioned metal and salt;
Described oxide is ZrO 2, ZnO, TiO 2, MnO 2, SnO, Al 2o 3, MgO, CuO, Eu 2o 3, Gd 2o 3, Tb 4o 7, Dy 2o 3, Ho 2o 3, Er 2o 3, Tm 2o 3, Yb 2o 3, Lu 2o 3, Nb 2o 5, Ag 2o.La 2O 3、Nd 2O 3；
Described salt is Zr (SO 4) 24H 2o, Zn (CH 3cOO) 22H 2o, TiCl 36H 2o, Mn (CH 3cOO) 24H 2o, C 4h 6mnO 4(Mn (CH 3cOO) 2), SnCl 2, AlCl 3, MgCl 2, CuCl 2, EuCl 3, Gd 2(HPO 3) 3(H 2o) 2, TbF 3, Dy 3al 5o 12, C 4h 6o 4mg4H 2o.
2. a preparation method for lithium ion battery anode material composite lithium iron phosphate, comprises the following steps:
One, preparing TiC, is that Ti and the C powder of 98.5 ~ 99.9%, granularity < 1 μm is mixed to get mixture in the ratio 1:1 of amount of substance by purity; Under 100 ~ 400rpm rotating speed, wet ball grinding 2 ~ 20h, obtains slurry; After drying slurry, at 240 ~ 360MPa forming under the pressure, pressurize 3 ~ 5min, obtain green body cylinders, by base substrate with the programming rate of 2 ~ 20 DEG C/min, from room temperature to 1800 ~ 2400 DEG C, roasting 1 ~ 10h, after naturally cooling to room temperature, being crushed to granularity is nanoscale or submicron order, obtains TiC;
TiC is used for adding in step 2 or step 7, and carry out coated to the LiFePO4 of doping, the TiC quality added is 0.1 ~ 30% of alloy and LiFePO4 quality sum;
Two, by the lithium dihydrogen phosphate of purity >=99.9% and the source of iron of purity >=99.5%, in the ratio 0.90 ~ 1.20:1 of amount of substance, be mixed to get raw material, add the alloy of material quality 0.01 ~ 5.3%, rotating speed is 100 ~ 400rpm, wet ball grinding 2 ~ 36h, to nanoscale or submicron order, obtains ball milling slurry;
Described source of iron is ferrous oxalate, di-iron trioxide, ferrous acetate, ferric nitrate, iron hydroxide, tri-iron tetroxide, ferrous oxide or ferrous hydroxide;
Described alloy is more than one in Zr, Zn, Ti, Mn, Sn, Al, Mg, Cu, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ag, Nb, lanthanum rich mischmetal Ml, cerium-rich mischmetal Mm, the oxide of aforementioned metal and salt;
Described oxide is ZrO 2, ZnO, TiO 2, MnO 2, SnO, Al 2o 3, MgO, CuO, Eu 2o 3, Gd 2o 3, Tb 4o 7, Dy 2o 3, Ho 2o 3, Er 2o 3, Tm 2o 3, Yb 2o 3, Lu 2o 3, Nb 2o 5, Ag 2o, La 2o 3, Nd 2o 3;
Described salt is Zr (SO 4) 24H 2o, Zn (CH 3cOO) 22H 2o, TiCl 36H 2o, Mn (CH 3cOO) 24H 2o, C 4h 6mnO 4(Mn (CH 3cOO) 2), SnCl 2, AlCl 3, MgCl 2, CuCl 2, EuCl 3, Gd 2(HPO 3) 3(H 2o) 2, TbF 3, Dy 3al 5o 12, C 4h 6o 4mg4H 2o;
Three, ball milling slurry is dried;
Four, by dry thing ball milling 1 ~ 10h under 100 ~ 400rpm rotating speed, precursor is obtained;
Five, presoma is warmed up to 200 ~ 400 DEG C from room temperature with the programming rate of 2 ~ 5 DEG C, pre-burning 2 ~ 12h, is then warmed up to 500 ~ 800 DEG C with the programming rate of 2 ~ 5 DEG C, constant temperature 8 ~ 36h, naturally cools to room temperature;
Six, ball milling or pulverizing is 0.2 ~ 40 μm to granularity;
Seven, carry out mechanical jolt ramming process, obtain lithium ion battery anode material composite lithium iron phosphate.
3. the preparation method of lithium ion battery anode material composite lithium iron phosphate according to claim 2, it is characterized in that: described step one wet ball grinding is 1:2 ~ 10 by the mass ratio of mixture and ball milling solvent, the mass ratio of mixture and ball-milling medium is 1:3 ~ 5.
4. the preparation method of lithium ion battery anode material composite lithium iron phosphate according to claim 2, is characterized in that: described step one green body cylinders diameter 20mm, high 100mm.
5. the preparation method of lithium ion battery anode material composite lithium iron phosphate according to claim 2, is characterized in that: base substrate is 0.4 ~ 1m at flow by described step one 3/ h.M 3argon gas, carbon dioxide, heat up under helium or nitrogen protection, roasting.
6. the preparation method of lithium ion battery anode material composite lithium iron phosphate according to claim 2, it is characterized in that: described step 2 wet ball grinding adds the dispersant of alloy and material quality sum 0.5 ~ 5 times, is 1:3 ~ 5 by the mass ratio of abrasive material and ball-milling medium.
7. the preparation method of lithium ion battery anode material composite lithium iron phosphate according to claim 2, is characterized in that: described step 3 is dried and adopted stirring and drying, spraying dry or flash distillation, and the dry matter amount water content obtained is less than 1%.
8. the preparation method of lithium ion battery anode material composite lithium iron phosphate according to claim 2, is characterized in that: presoma is 0.4 ~ 1m at flow by described step 5 3/ h.M 3non-oxidizing gas CO, CO 2, He, Ar or N 2under atmosphere protection, pre-burning, constant temperature.
9. the preparation method of lithium ion battery anode material composite lithium iron phosphate according to claim 2, is characterized in that: described step 6 ball milling ball milling 1 ~ 10h under 100 ~ 400rpm rotating speed.
10. the lithium ion battery of a lithium ion battery anode material composite lithium iron phosphate, be provided with positive pole, it is characterized in that: described positive electrode active materials is with the LiFePO4 doped with alloy for matrix, and matrix is coated with TiC coating layer, the quality of coating layer is 0.1 ~ 30% of substrate quality; Described alloy quality is 0.01 ~ 5% of LiFePO4 quality;
Described alloy is more than one in Zr, Zn, Ti, Mn, Sn, Al, Mg, Cu, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ag, Nb, lanthanum rich mischmetal Ml, cerium-rich mischmetal Mm, the oxide of aforementioned metal and salt;
Described oxide is ZrO 2, ZnO, TiO 2, MnO 2, SnO, Al 2o 3, MgO, CuO, Eu 2o 3, Gd 2o 3, Tb 4o 7, Dy 2o 3, Ho 2o 3, Er 2o 3, Tm 2o 3, Yb 2o 3, Lu 2o 3, Nb 2o 5, Ag 2o.La 2O 3、Nd 2O 3；
Described salt is Zr (SO 4) 24H 2o, Zn (CH 3cOO) 22H 2o, TiCl 36H 2o, Mn (CH 3cOO) 24H 2o, C 4h 6mnO 4(Mn (CH 3cOO) 2), SnCl 2, AlCl 3, MgCl 2, CuCl 2, EuCl 3, Gd 2(HPO 3) 3(H 2o) 2, TbF 3, Dy 3al 5o 12, C 4h 6o 4mg4H 2o.
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