CN105489864A - Titanium sub-oxide coated and modified lithium iron phosphate composite material and preparation method thereof - Google Patents
Titanium sub-oxide coated and modified lithium iron phosphate composite material and preparation method thereof Download PDFInfo
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- CN105489864A CN105489864A CN201610022653.9A CN201610022653A CN105489864A CN 105489864 A CN105489864 A CN 105489864A CN 201610022653 A CN201610022653 A CN 201610022653A CN 105489864 A CN105489864 A CN 105489864A
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- 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
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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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- 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 provides a titanium sub-oxide coated and modified lithium iron phosphate composite material and a preparation method thereof. The surface of lithium iron phosphate is coated with titanium sub-oxide, the molecular formula of the titanium sub-oxide coated and modified lithium iron phosphate composite material is LiFePO4/Ti4O7, and the covering amount of titanium sub-oxide is 5%-10%. With the adoption of the technical scheme provided by the invention, the lithium iron phosphate material is coated with and modified by titanium sub-oxide with high conductivity, so that the high-rate charge/discharge capacity of lithium iron phosphate is obviously improved, the cycling capacity degradation of lithium iron phosphate at high current density is reduced, and the high-rate cycle performance of lithium iron phosphate is further improved; at the same time, the internal resistance of a battery is effectively reduced, the specific power of a lithium iron phosphate power battery is increased, the adaptation to the deep cycle requirement of the power battery is facilitated, the preparation process is simple and convenient, and the composite material is also suitable for large-scale industrial production.
Description
Technical field
The invention belongs to lithium ion field of material technology, particularly relate to a kind of sub-titanium-oxide-coated modified phosphate iron lithium composite material and preparation method thereof.
Background technology
Commercial lithium iron battery positive electrode is LiFePO4, have up to the theoretical capacity of 170mAh/g, good cycle performance and security performance, become the main force of power lithium-ion battery, but there is lower lithium ion diffusion rate (10 due to LiFePO4
-14~ 10
-10cm
2/ s) and low electronic conductivity (<10
-9s/cm), LiFePO4 is made can not to meet the user demand of electrokinetic cell.The conventional electric conductivity adopting the coated means of carbon to improve LiFePO4 more, but carbon ratio surface area is too large, dispersed bad, and resistance to corrosion is poor, causes the decay of battery capacity.And along with electrokinetic cell is to the requirement of high-energy-density, high power density, the performance such as conductivity, circulation volume maintenance, high rate charge-discharge performance, quick charge for LiFePO4 need further raising.
Summary of the invention
For above technical problem, the invention discloses a kind of sub-titanium-oxide-coated modified phosphate iron lithium composite material and preparation method thereof, the conductive network distributing homogeneity of described sub-titanium-oxide-coated modified phosphate iron lithium composite material is better, the specific power be conducive to reducing the internal resistance of cell, improving electrokinetic cell, be conducive to the decay reducing battery material circulation volume simultaneously, improve the large high rate performance of material.
To this, the technical solution used in the present invention is:
A kind of sub-titanium-oxide-coated modified phosphate iron lithium composite material, described LiFePO4 Surface coating has sub-titanium oxide, and the molecular formula of described sub-titanium-oxide-coated modified phosphate iron lithium composite material is LiFePO
4/ Ti
4o
7, the covering amount of described sub-titanium oxide is 5%-10%.
The invention provides a kind of iron phosphate compound anode material of lithium of sub-titanium-oxide-coated, sub-titanium oxide easily disperses, and its effect is more coated than carbon better, and conductive network distribution is more even; Sub-titanium oxide conductivity and decay resistance are all better than carbon, and stable chemical nature, not passivation under high current density or peracid condition, do not corrode, and then make effectively to reduce the internal resistance of cell, improve the specific power of electrokinetic cell, adapt to electrokinetic cell deep-cycle demand; Reduce the decay of battery material circulation volume, improve the large high rate performance of material, charging rate can increase substantially simultaneously.
As a further improvement on the present invention, it adopts following steps to prepare:
Step S1: prepare LiFePO4;
Step S2: butyl titanate is joined in absolute ethyl alcohol and stirs, then add acetic acid, stir; Then add deionized water, stir 0.5 ~ 2h, obtain yellow sol solution, then add thickener, stir and obtain titanium oxide sol; Wherein, the volume ratio of described acetic acid and butyl titanate is 1:(4 ~ 6), the consumption of described deionized water is 1/10 of butyl titanate volume; Preferably, the volume ratio of described acetic acid and butyl titanate is 1:5.
Step S3: LiFePO4 is joined in the titanium oxide sol of step S2, described LiFePO4 is 5:1-10:1 with the amount of substance ratio of the butyl titanate in titanium oxide sol, stirs, vacuum filtration, vacuumize 1-4h; Add reducing substances and carry out reduction reaction, and in 800 ~ 900 DEG C of heating 10 ~ 15h, naturally cool, obtain the composite ferric lithium phosphate material of sub-titanium-oxide-coated; Wherein, described reducing substances is KBH
4, HCHO, NaH
2pO
3, liquefied ammonia lithium, H
2, at least one in hydrazine.
As a further improvement on the present invention, in step S3, described LiFePO4 is 6:1-8:1 with the amount of substance ratio of the butyl titanate in titanium oxide sol.
As a further improvement on the present invention, in step S1, described LiFePO4 is prepared according to following steps: be 1:(1.00 ~ 1.03 by source of iron, lithium source, phosphorus source according to the mol ratio of Fe:Li:P): 1 takes raw material, described source of iron, lithium source, phosphorus source raw material are joined in ethanol medium, ball milling mixes, then 600 ~ 700 DEG C of heating 8 ~ 12h in inert atmosphere stove, cooling, grind, obtain iron phosphate powder;
As a further improvement on the present invention, described source of iron, lithium source, phosphorus source raw material join in ethanol medium, first ball milling mixing 3 ~ 6h, in 70 ~ 90 DEG C of oven dry, cooling, continue ball milling 1 ~ 3h and mix.
As a further improvement on the present invention, described source of iron is at least one in ferrous oxalate or ferrous citrate; Described phosphorus source is at least one in diammonium hydrogen phosphate, lithium dihydrogen phosphate, ammonium dihydrogen phosphate; Described lithium source is at least one in lithium carbonate or lithium dihydrogen phosphate.
As a further improvement on the present invention, in step S2, described thickener is the one in PEG or PVP;
As a further improvement on the present invention, described inert atmosphere is argon gas or helium atmosphere.
The invention also discloses a kind of preparation method of sub-titanium-oxide-coated modified phosphate iron lithium composite material as above, comprise the following steps:
Step S1: be 1:(1.00 ~ 1.03 according to the mol ratio of Fe:Li:P by source of iron, lithium source, phosphorus source): 1 takes raw material, described source of iron, lithium source, phosphorus source raw material are joined in ethanol medium, ball milling mixes, then 600 ~ 700 DEG C of heating 8 ~ 12h in inert atmosphere stove, cooling, grind, obtain iron phosphate powder; Wherein, described source of iron is at least one in ferrous oxalate or ferrous citrate; Described phosphorus source is at least one in diammonium hydrogen phosphate, lithium dihydrogen phosphate, ammonium dihydrogen phosphate; Described lithium source is at least one in lithium carbonate or lithium dihydrogen phosphate;
Step S2: butyl titanate is joined in absolute ethyl alcohol and stirs, then add acetic acid, stir; Then add deionized water, stir 0.5 ~ 2h, obtain yellow sol solution, then add thickener, stir and obtain titanium oxide sol; Wherein, the volume ratio of described acetic acid and butyl titanate is 1:(4 ~ 6), the consumption of described deionized water is 1/10 of butyl titanate volume; Preferably, the volume ratio of described acetic acid and butyl titanate is 1:5.
Step S3: LiFePO4 is joined in the titanium oxide sol of step S2, described LiFePO4 is 5:1-10:1 with the amount of substance ratio of the butyl titanate in titanium oxide sol, stirs, vacuum filtration, vacuumize 1-4h; With reducing substances reduction, in 800 ~ 900 DEG C of heating 10 ~ 15h, naturally cool, obtain the composite ferric lithium phosphate material of sub-titanium-oxide-coated, the covering amount of sub-titanium oxide is 5%-10%; Wherein, described reducing substances is KBH
4, HCHO, NaH
2pO
3, liquefied ammonia lithium, H
2, at least one in hydrazine.
Preferably, in step S3, described LiFePO4 is 6:1-8:1 with the amount of substance ratio of the butyl titanate in titanium oxide sol.
Preferably, in step S2, described thickener is the one in PEG or PVP;
Preferably, described inert atmosphere is argon gas or helium atmosphere.
Compared with prior art, beneficial effect of the present invention is:
Technical scheme of the present invention have employed the sub-titanium oxide with high conductivity and carries out coating modification to LiFePO 4 material, the high rate charge-discharge ability significantly improving LiFePO4, the decay reducing LiFePO4 circulation volume under high current density, improves its high rate cyclic performance; Meanwhile, effectively reduce the internal resistance of cell, improve the specific power of lithium iron phosphate dynamic battery, adapt to electrokinetic cell deep-cycle demand.Compared with common carbon coating technology means, in technical solution of the present invention, adopt the LiFePO after sub-titanium-oxide-coated
4significantly improve high rate charge-discharge ability, cell testing results: current density 1C, 2C, 5C, 10C capacity respectively can up to 158mAh/g, 151mAh/g, 139mAh/g, 110mAh/g, and 5C circulates 300 weeks capability retentions more than 85%.And the preparation technology of technical solution of the present invention is easy, be applicable to industrialization large-scale production.
Embodiment
Be below specific embodiment of the invention case, illustrate the present invention further in conjunction with case study on implementation, but the present invention be not limited to case study on implementation.
Embodiment 1
A kind of sub-titanium-oxide-coated modified phosphate iron lithium composite material, its molecular formula is LiFePO
4/ Ti
4o
7, the covering amount of sub-titanium oxide is 5%.Prepared by employing following steps:
Step S1: be first that 1:1:1 respectively takes raw material ferrous oxalate 143.86g, lithium dihydrogen phosphate 103.93g by ferrous oxalate, lithium dihydrogen phosphate according to the mol ratio of Fe:Li:P, ferrous oxalate, lithium dihydrogen phosphate are placed in ethanol medium ball milling mixing 4h, in 80 DEG C of oven dry, naturally cool, continue ball milling 2h to mix, then 600 DEG C of heating 12h in Ar gas atmosphere furnace, obtain iron phosphate powder after cooling naturally.
Step S2: under normal temperature, butyl titanate and water are scattered in absolute ethyl alcohol according to the volume ratio of 1:5, the acetic acid being equivalent to butyl titanate 1/5 volume is dripped in stirring, continue to stir the yellow solution that 20min obtains homogeneous transparent, drip the deionized water being equivalent to butyl titanate 1/10 volume, continue to stir 1h and obtain yellow sol solution, add certain proportion thickener PVP, stir and obtain titanium oxide sol;
Step S3: add LiFePO 4 powder in titanium oxide sol, after stirring, according to M(HCHO than the ratio of 10:1 according to LiFePO4 and the amount of substance of butyl titanate): M(TiO
2the ratio of)=1:2 adds certain HCHO gradually and reduces, vacuum filtration, 120 DEG C of vacuumize 3h; Then 800 DEG C of insulation 15h in Ar gas atmosphere furnace, naturally cool, obtain the composite ferric lithium phosphate material of sub-titanium-oxide-coated, wherein, the covering amount of sub-titanium oxide is 5%.
Above-mentioned composite material, binding agent PVDF and the conductive agent acetylene black ratio in 85:10:5 is fully mixed in solvent (1-METHYLPYRROLIDONE), be applied on aluminium foil by gained slurry, after 120 DEG C of vacuumizes, pole piece is cut into circular electrode as work electrode.In the glove box being full of argon gas, using metal lithium sheet as to electrode, Celgard2400 is the LiPF of barrier film, 1mol/L
6/ EC-EMC-DMC(volume ratio is 1:1:1) be electrolyte, be assembled into button cell, carry out electrochemical property test; Electrochemical results; 1C, 2C, 5C, 10C, 20C capacity is still respectively up to 153mAh/g, 146mAh/g, 128mAh/g, 103mAh/g.5C circulates 300 weeks capability retentions 85.7%.
Embodiment 2
A kind of sub-titanium-oxide-coated modified phosphate iron lithium composite material, adopts following steps preparation:
Step S1: be first that 1:1.02:1 respectively takes raw material ferrous citrate 246g, lithium carbonate 37.68g, diammonium hydrogen phosphate 132.06g by ferrous citrate, lithium carbonate, diammonium hydrogen phosphate according to Fe:Li:P mol ratio, above-mentioned three kinds of raw materials are placed in ethanol medium ball milling mixing 4h, in 80 DEG C of oven dry, naturally cool, continue ball milling 2h to mix, then 650 DEG C of high-temperature heating 10h in Ar gas atmosphere furnace, obtain iron phosphate powder after cooling naturally.
Step S2: under normal temperature, butyl titanate and water are scattered in absolute ethyl alcohol according to the volume ratio of 1:5, the acetic acid being equivalent to butyl titanate 1/5 volume is dripped in stirring, continue to stir the yellow solution that 20min obtains homogeneous transparent, drip the deionized water being equivalent to butyl titanate 1/10 volume, continue to stir 1h and obtain yellow sol solution, add certain proportion thickener PVP, stir and obtain titanium oxide sol.
Step S3: than the ratio of 8:1, LiFePO 4 powder is joined in titanium oxide sol, after stirring, according to M(hydrazine according to LiFePO4 and the amount of substance of butyl titanate): M(TiO
2the ratio of)=1:4 adds certain hydrazine gradually and reduces, vacuum filtration, 120 DEG C of vacuumize 2h; Then 850 DEG C of heating 12h in Ar gas atmosphere furnace, naturally cool, obtain the composite ferric lithium phosphate material of sub-titanium-oxide-coated, wherein, the covering amount of sub-titanium oxide is 6.2%;
Above-mentioned composite material is assembled into button cell according to the method for embodiment 1, Electrochemical results; 1C, 2C, 5C, 10C, 20C capacity is respectively up to 155mAh/g, 147mAh/g, 131mAh/g, 108mAh/g.5C circulates 300 weeks capability retentions 86.3%.
Embodiment 3
A kind of sub-titanium-oxide-coated modified phosphate iron lithium composite material, adopts following steps preparation:
Step S1: be first that 1.00:1.03:1.00 respectively takes raw material ferrous oxalate 143.86g, lithium carbonate 38.79g, ammonium dihydrogen phosphate 115.03g by ferrous oxalate, lithium carbonate, ammonium dihydrogen phosphate according to Fe:Li:P mol ratio, by above-mentioned three kinds of raw materials ball milling mixing 4h in ethanol medium, in 80 DEG C of oven dry, naturally cool, continue ball milling 2h to mix, then 700 DEG C of high-temperature heating 8h in Ar gas atmosphere furnace, obtain iron phosphate powder after cooling naturally.
Step S2: under normal temperature, butyl titanate and water are scattered in absolute ethyl alcohol according to the volume ratio of 1:5, the acetic acid being equivalent to butyl titanate 1/5 volume is dripped in stirring, continue to stir the yellow solution that 20min obtains homogeneous transparent, drip the deionized water being equivalent to butyl titanate 1/10 volume, continue to stir 1h and obtain yellow sol solution, add certain proportion thickener PEG, stir and obtain titanium oxide sol.
Step S3: add LiFePO 4 powder than the ratio of 5:1, after stirring, according to M(Li according to LiFePO4 and the amount of substance of butyl titanate): M(TiO
2the ratio of)=1:2 adds certain liquefied ammonia lithium gradually and reduces, vacuum filtration, 120 DEG C of vacuumize 3h; In H
2in/Ar mixed atmosphere stove, in 900 DEG C of heating 10h, naturally cool, obtain the composite ferric lithium phosphate material of sub-titanium-oxide-coated, the covering amount of sub-titanium oxide is 10%.
Above-mentioned composite material is assembled into button cell according to the method for embodiment 1, Electrochemical results; Current density 1C, 2C, 5C, 10C capacity reach 158mAh/g, 151mAh/g, 139mAh/g, 112mAh/g respectively, and 5C circulates 300 weeks capability retentions 87.6%.
Embodiment 4
A kind of sub-titanium-oxide-coated modified phosphate iron lithium composite material, adopts following steps preparation:
Step S1: be first that 1.00:1.02:1.00 respectively takes raw material ferrous citrate 246g, lithium carbonate 37.68g, diammonium hydrogen phosphate 132.06g by ferrous citrate, lithium carbonate, diammonium hydrogen phosphate according to the mol ratio of Fe:Li:P, by above-mentioned three kinds of raw materials ball milling mixing 4h in ethanol medium, in 80 DEG C of oven dry, naturally cool, continue ball milling 2h to mix, then 650 DEG C of high-temperature heating 10h in Ar gas atmosphere furnace, obtain iron phosphate powder after cooling naturally.
Step S2: under normal temperature, butyl titanate is scattered in absolute ethyl alcohol according to the volume ratio of 1:5, the acetic acid being equivalent to butyl titanate 1/5 volume is dripped in stirring, continue to stir the yellow solution that 20min obtains homogeneous transparent, drip the deionized water being equivalent to butyl titanate 1/10 volume, continue to stir 1h and obtain yellow sol solution, add certain proportion thickener PVP, stir and obtain titanium oxide sol;
Step S3: add LiFePO 4 powder than the ratio of 8:1, after stirring, according to M(KBH according to LiFePO4 and the amount of substance of butyl titanate
4): M(TiO
2the ratio of)=1:16 adds certain KBH gradually
4reduce, vacuum filtration, 120 DEG C of vacuumize 2h; Then in H
2in/Ar mixed atmosphere stove, in 850 DEG C of heating 12h, naturally cool, obtain the composite ferric lithium phosphate material of sub-titanium-oxide-coated, the covering amount of sub-titanium oxide is 6.2%;
Above-mentioned composite material is assembled into button cell according to the method for embodiment 1, Electrochemical results; 1C, 2C, 5C, 10C, 20C capacity is respectively up to 156mAh/g, 149mAh/g, 134mAh/g, 110mAh/g.5C circulates 300 weeks capability retentions 87.1%.
Embodiment 5
A kind of sub-titanium-oxide-coated modified phosphate iron lithium composite material, adopts following steps preparation:
Step S1: be first that 1:1:1 respectively takes raw material ferrous oxalate 143.86g, lithium dihydrogen phosphate 103.93g by ferrous oxalate, lithium dihydrogen phosphate according to Fe:Li:P mol ratio, by these three kinds of raw materials ball milling mixing 4h in ethanol medium, in 80 DEG C of oven dry, naturally cool, continue ball milling 2h to mix, then 600 DEG C of high-temperature heating 12h in Ar gas atmosphere furnace, obtain iron phosphate powder after cooling naturally.
Step S2: under normal temperature, butyl titanate is scattered in absolute ethyl alcohol according to the volume ratio of 1:5, the acetic acid being equivalent to butyl titanate 1/5 volume is dripped in stirring, continue to stir the yellow solution that 20min obtains homogeneous transparent, drip the deionized water being equivalent to butyl titanate 1/10 volume, continue to stir 1h and obtain yellow sol solution, add certain proportion thickener PEG, stir and obtain titanium oxide sol.
Step S3: add LiFePO 4 powder than the ratio of 10:1, after stirring, according to M(NaH according to LiFePO4 and the amount of substance of butyl titanate
2pO
3): M(TiO
2the ratio of)=1:2 adds certain NaH gradually
2pO
3reduce, vacuum filtration, 120 DEG C of vacuumize 3h; Then in H
2in/Ar mixed atmosphere stove, in 800 DEG C of insulation 15h, naturally cool, obtain the composite ferric lithium phosphate material of sub-titanium-oxide-coated, the covering amount of sub-titanium oxide is 5%;
Above-mentioned composite material is assembled into button cell according to the method for embodiment 1, Electrochemical results; 1C, 2C, 5C, 10C, 20C capacity is respectively up to 155mAh/g, 149mAh/g, 133mAh/g, 109mAh/g.5C circulates 300 weeks capability retentions 86.7%.
Comparative example 1
The preparation of iron phosphate powder is with embodiment 3.
Conductive carbon is mixed, then in H with the mass ratio ball milling of iron phosphate powder according to 1:9
2900 DEG C of heating 10h in/Ar mixed atmosphere stove, naturally obtain the coated composite ferric lithium phosphate material of carbon after cooling, covering amount is 10%.
Button cell is assembled with embodiment 1, Electrochemical results; 1C, 2C, 5C, 10C, 20C discharge capacity is respectively 158mAh/g, 147mAh/g, 126mAh/g, 106.3mAh/g, and the 5C 300 weeks capability retentions that circulate are 75.3%.
Visible with the performance data of comparative example 1 by embodiment 1 ~ 5, technical solution of the present invention adopts the LiFePO after sub-titanium-oxide-coated
4significantly improve its high rate charge-discharge ability, reduce the decay of battery material circulation volume, improve the high rate charge-discharge performance of material, 5C circulates 300 weeks capability retentions more than 85% simultaneously.
Should be understood that the experimental technique of unreceipted actual conditions in embodiment, usually conveniently condition, or according to the condition that manufacturer advises.Unless otherwise indicated, otherwise number and percentage are weight portion and percentage by weight.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, some simple deduction or replace can also be made, all should be considered as belonging to protection scope of the present invention.
Claims (9)
1. a sub-titanium-oxide-coated modified phosphate iron lithium composite material, is characterized in that: described LiFePO4 Surface coating has sub-titanium oxide, and the molecular formula of described sub-titanium-oxide-coated modified phosphate iron lithium composite material is LiFePO
4/ Ti
4o
7, the covering amount of described sub-titanium oxide is 5%-10%.
2. sub-titanium-oxide-coated modified phosphate iron lithium composite material according to claim 1, is characterized in that: it adopts following steps to prepare:
Step S1: prepare LiFePO4;
Step S2: butyl titanate is joined in absolute ethyl alcohol and stirs, then add acetic acid, stir; Then add deionized water, stir 0.5 ~ 2h, obtain yellow sol solution, then add thickener, stir and obtain titanium oxide sol; Wherein, the volume ratio of described acetic acid and butyl titanate is 1:(4 ~ 6), the consumption of described deionized water is 1/10 of butyl titanate volume;
Step S3: LiFePO4 is joined in the titanium oxide sol of step S2, described LiFePO4 is 5:1-10:1 with the amount of substance ratio of the butyl titanate in titanium oxide sol, stirs, vacuum filtration, vacuumize 1-4h; Add reducing substances and carry out reduction reaction, and in 800 ~ 900 DEG C of heating 10 ~ 15h, naturally cool, obtain the composite ferric lithium phosphate material of sub-titanium-oxide-coated; Wherein, described reducing substances is KBH
4, HCHO, NaH
2pO
3, liquefied ammonia lithium, H
2, at least one in hydrazine.
3. sub-titanium-oxide-coated modified phosphate iron lithium composite material according to claim 2, is characterized in that: in step S3, and described LiFePO4 is 6:1-8:1 with the amount of substance ratio of the butyl titanate in titanium oxide sol.
4. sub-titanium-oxide-coated modified phosphate iron lithium composite material according to claim 2, it is characterized in that: in step S1, described LiFePO4 is prepared according to following steps: be 1:(1.00 ~ 1.03 by source of iron, lithium source, phosphorus source according to the mol ratio of Fe:Li:P): 1 takes raw material, described source of iron, lithium source, phosphorus source raw material are joined in ethanol medium, ball milling mixes, then 600 ~ 700 DEG C of heating 8 ~ 12h in inert atmosphere stove, cooling, grind, obtain iron phosphate powder.
5. sub-titanium-oxide-coated modified phosphate iron lithium composite material according to claim 4, it is characterized in that: described source of iron, lithium source, phosphorus source raw material join in ethanol medium, first ball milling mixing 3 ~ 6h, in 70 ~ 90 DEG C of oven dry, cooling, continues ball milling 1 ~ 3h and mixes.
6. sub-titanium-oxide-coated modified phosphate iron lithium composite material according to claim 4, is characterized in that: described source of iron is at least one in ferrous oxalate or ferrous citrate; Described phosphorus source is at least one in diammonium hydrogen phosphate, lithium dihydrogen phosphate, ammonium dihydrogen phosphate; Described lithium source is at least one in lithium carbonate or lithium dihydrogen phosphate.
7. the sub-titanium-oxide-coated modified phosphate iron lithium composite material according to claim 2 ~ 6 any one, it is characterized in that: in step S2, described thickener is the one in PEG or PVP.
8. sub-titanium-oxide-coated modified phosphate iron lithium composite material according to claim 7, is characterized in that: described inert atmosphere is argon gas or helium atmosphere.
9. a preparation method for the sub-titanium-oxide-coated modified phosphate iron lithium composite material as described in claim 1 ~ 8 any one, is characterized in that, comprise the following steps:
Step S1: be 1:(1.00 ~ 1.03 according to the mol ratio of Fe:Li:P by source of iron, lithium source, phosphorus source): 1 takes raw material, described source of iron, lithium source, phosphorus source raw material are joined in ethanol medium, ball milling mixes, then 600 ~ 700 DEG C of heating 8 ~ 12h in inert atmosphere stove, cooling, grind, obtain iron phosphate powder; Wherein, described source of iron is at least one in ferrous oxalate or ferrous citrate; Described phosphorus source is at least one in diammonium hydrogen phosphate, lithium dihydrogen phosphate, ammonium dihydrogen phosphate; Described lithium source is at least one in lithium carbonate or lithium dihydrogen phosphate;
Step S2: butyl titanate is joined in absolute ethyl alcohol and stirs, then add acetic acid, stir; Then add deionized water, stir 0.5 ~ 2h, obtain yellow sol solution, then add thickener, stir and obtain titanium oxide sol; Wherein, the volume ratio of described acetic acid and butyl titanate is 1:(4 ~ 6), the consumption of described deionized water is 1/10 of butyl titanate volume;
Step S3: LiFePO4 is joined in the titanium oxide sol of step S2, described LiFePO4 is 5:1-10:1 with the amount of substance ratio of the butyl titanate in titanium oxide sol, stirs, vacuum filtration, vacuumize 1-4h; With reducing substances reduction, in 800 ~ 900 DEG C of heating 10 ~ 15h, naturally cool, obtain the composite ferric lithium phosphate material of sub-titanium-oxide-coated; Wherein, described reducing substances is KBH
4, HCHO, NaH
2pO
3, liquefied ammonia lithium, H
2, at least one in hydrazine.
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| CN105932261A (en) * | 2016-06-30 | 2016-09-07 | 湖南桑顿新能源有限公司 | Lithium manganate cathode material and preparation method thereof |
| CN105977466A (en) * | 2016-06-30 | 2016-09-28 | 湖南桑顿新能源有限公司 | Conductive oxide coated lithium ion battery tri-element anode material and preparation method thereof |
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| CN106532003A (en) * | 2016-12-07 | 2017-03-22 | 西南石油大学 | Ti4O7-coated modified lithium titanate composite material and preparation method thereof |
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| CN105977466A (en) * | 2016-06-30 | 2016-09-28 | 湖南桑顿新能源有限公司 | Conductive oxide coated lithium ion battery tri-element anode material and preparation method thereof |
| CN105932261A (en) * | 2016-06-30 | 2016-09-07 | 湖南桑顿新能源有限公司 | Lithium manganate cathode material and preparation method thereof |
| CN106299340A (en) * | 2016-10-11 | 2017-01-04 | 苏州大学 | A kind of preparation method of modified tertiary cathode material |
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| CN109449417A (en) * | 2018-11-01 | 2019-03-08 | 中科廊坊过程工程研究院 | A kind of phosphoric acid ferrisodium composite positive pole and its preparation method and application |
| CN109742332A (en) * | 2018-11-23 | 2019-05-10 | 颍上北方动力新能源有限公司 | A kind of production method of positive plate of lithium battery |
| CN110112387A (en) * | 2019-05-07 | 2019-08-09 | 湖南金富力新能源股份有限公司 | A kind of positive electrode and preparation method thereof that Asia titanium-oxide-coated is modified |
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| CN110165182A (en) * | 2019-05-30 | 2019-08-23 | 渤海大学 | One kind coating TiO for the surface potassium sulphur cell positive electrode TiC2-xThe preparation method and application of/sulphur combination electrode material |
| CN110176596A (en) * | 2019-06-17 | 2019-08-27 | 启东启澳新材料科技发展有限公司 | A method of improving lithium battery anode coating material chemical property |
| CN110550615A (en) * | 2019-10-14 | 2019-12-10 | 王敏 | Preparation method of high-energy-density lithium iron phosphate |
| CN111170294A (en) * | 2020-01-19 | 2020-05-19 | 江苏乐能电池股份有限公司 | Preparation method of low-cost lithium iron phosphate composite material |
| CN112340817A (en) * | 2020-11-09 | 2021-02-09 | 南通科技职业学院 | Nano titanium protoxide catalytic electrode material and preparation method thereof |
| CN112340817B (en) * | 2020-11-09 | 2022-11-29 | 南通科技职业学院 | Nano titanium protoxide catalytic electrode material and preparation method thereof |
| CN112713272A (en) * | 2020-12-18 | 2021-04-27 | 浙江金鹰瓦力新能源科技有限公司 | Preparation method of modified lithium battery positive electrode material |
| CN113423255A (en) * | 2021-06-09 | 2021-09-21 | 西北工业大学 | Core-shell structure Ti4O7Magnetic metal composite absorbent and preparation method thereof |
| CN114361396A (en) * | 2021-12-21 | 2022-04-15 | 重庆东星炭素材料有限公司 | Preparation method of new energy battery electrode |
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