CN107834070A - A kind of lithium iron phosphate positive material, lithium ion battery and preparation method thereof - Google Patents
A kind of lithium iron phosphate positive material, lithium ion battery and preparation method thereof Download PDFInfo
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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
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- 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
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
The present invention relates to a kind of lithium iron phosphate positive material, lithium ion battery and preparation method thereof, belong to technical field of lithium batteries.Comprise the following steps：1st step, by lithium hydroxide, 25~45 parts mix with 25~30 parts of water, 9~15 parts of ethanol, and 12~16 parts of ionic liquid for adding silane coupler grafting is modified reaction；2nd step, 110~140 parts of ferric phosphate is formulated as the aqueous solution that solid content is 30~50wt.%, adds 2~4% anion surfactant of ferric phosphate weight, after mixed at high speed, be slowly added dropwise in the reactant that the 1st step obtains, stir, obtain slurry；3rd step, slurry is obtained into LiFePO 4 material after being spray-dried, sintering.LiFePO 4 material provided by the invention, when it is applied to the positive electrode of lithium ion battery, there is the advantages of capacitance is big, discharging efficiency is high, circulation discharge time is more.
Description
Technical field
The present invention relates to a kind of lithium iron phosphate positive material, lithium ion battery and preparation method thereof, belong to lithium battery technology
Field.
Background technology
When being charged to battery, the lithium-containing compound of positive pole has lithium ion abjection, and lithium ion passes through electrolyte movement
To negative pole.The Carbon Materials of negative pole are in layer structure, and it has many micropores, reach the Lithium-ion embeding of negative pole to the micropore of carbon-coating
In, embedded lithium ion is more, and charging capacity is higher.When discharging battery（I.e. we use the process of battery）, it is embedding
Lithium ion abjection in negative pole carbon-coating, moves back positive pole again.Return positive pole lithium ion it is more, discharge capacity is higher.We are logical
What often described battery capacity referred to is exactly discharge capacity.In the charge and discharge process of lithium ion battery, lithium ion is in from positive pole
The motion state of → negative pole → positive pole.This is just as a rocking chair, and the both ends of rocking chair are the two poles of the earth of battery, and lithium ion is just in rocking chair
Both ends move back and forth.So lithium ion battery is called rocking chair type battery.The main composition of lithium ion battery includes：1）Positive pole, it is
Active material, cobalt acid lithium, LiMn2O4, LiFePO4, lithium nickelate, nickle cobalt lithium manganate etc. are referred mainly to, conductive current collector typically uses
Aluminium foil of the thickness at 10~20 microns；（2）Barrier film, it is a kind of special plastic foil, lithium ion can be allowed to pass through but electronics
Insulator, mainly have two kinds of PE and PP and combinations thereof at present.Also a kind of inoganic solids barrier film, if aluminum oxide barrier film coating
It is a kind of inoganic solids barrier film,；（3）Negative pole, it is active material, refers mainly to the carbon materials of graphite, lithium titanate or approximate graphite-structure
Material, conductive current collector typically use thickness in the copper foil of 7-15 microns；（4）Electrolyte, generally organic system, such as it is dissolved with six
The carbonate-based solvent of lithium fluophosphate, some another polymer batteries use gel electrolyte；（5）Battery case, it is broadly divided into
Duricrust（Box hat, aluminum hull, nickel plating iron-clad etc.）And Soft Roll（Aluminum plastic film）Two kinds.The charging process of lithium ion battery is divided into two ranks
Section：Constant-current charging phase and constant-voltage power supply tapered charge stage.The excessive discharge and recharge of lithium ion battery can cause forever to both positive and negative polarity
Property damage.Over-discharge causes negative pole carbon plate Rotating fields to collapse, and collapsing can cause lithium ion in charging process not insert
Enter；Overcharging makes excessive Lithium-ion embeding negative pole carbon structure, and causes which part lithium ion can not again discharge.
Because the specific capacity of negative material in lithium ion battery and performance are far above positive electrode, therefore research more at present
Work is main to concentrate in the specific capacity and charge and discharge speed that improve positive electrode.So far, the conventional lithium ion of comparative maturity
The research of cell positive material concentrates on the transition metal oxide LiMO of stratiform2(M=Co, Ni, Mn etc.) and spinel-type
LiM2O2(M=Co, Ni, Mn etc.).LiCoO2It is earliest commercialized anode material for lithium-ion batteries, its theoretical specific capacity is high
(274mAh/g), open-circuit voltage are big, stable electrochemical property, and shortcoming is shortage of resources, expensive and poisonous, high temperature can occur
Blast.LiNiO2Specific capacity big (275mAh/g), cheap, shortcoming is that preparation technology is complicated, heat endurance is poor. LiMn2O4
Aboundresources, cheap, nontoxic, but its specific capacity is relatively low (148mAh/g), and capacity attenuation is fast under high temperature, the life-span is poor.Institute
A series of shortcomings of above material, to have had a strong impact on the application performance of these materials, and make these materials still in constantly grinding
The stage studied carefully and developed.LiFePO4, it has excellent chemical property, theoretical specific capacity 170mAh/g, to lithium platform electricity
Press as 3.4V, cost is cheap, environment-friendly, has extended cycle life, and security is good under high temperature, has taken into account Li2CoO2、LiNiO2、
LiVO2The major advantage of material, the positive electrode as lithium ion battery preferably solve cost, environment, safety problem, by
The extensive concern of people is arrived.LiFePO4Appearance be considered as " lithium ion battery one New Times arrive " mark.
CN103441271A discloses a kind of anions and canons codope lithium iron phosphate positive material, is magnesium, the phosphorus of fluorine codope
The compound of sour iron lithium and carbon, magnesium ion part substitute the iron ion position in LiFePO4 crystal, fluorine ion part substitution phosphorus
Phosphate ion position in sour iron lithium, its main component can be by LiFe1-xMgx(PO4)1-yF3y/ C is expressed, wherein 0.001≤x≤
0.1,0.001≤y≤0.1, high temperature solid-state legal system is passed through as raw material using lithium source, ferrous source, phosphorus source, magnesium source, Fluorine source and carbon source
It is standby.CN104659332A discloses a kind of high rate lithium iron phosphate cell positive pole, it is characterized in that：The afflux phosphor bodies of electrode are tool
Have the through-hole foam nickel of three-dimensional conductive skeleton structure, nickel foam conducting matrix grain surface coated with can electronic conduction protective layer, collection
Bodies of fluid is the nickel foam for having three-dimensional conductive skeleton structure, and the porosity of nickel foam is 50~98%, and through-hole rate is more than
98%, protective layer is the conductive coating of the pvdf containing 5%~95% conducting particles or polyacrylic acid；Conducting particles is less than for particle diameter
One kind in 5um conductive black, graphite and aluminium powder.CN102569814A discloses one kind and is used as positive electrode material of lithium secondary cell
Rare-earth type lithium iron phosphate and preparation method thereof.The rare-earth type lithium iron phosphate contains the LiFePO4 of 100 molfractions, and 3.9
The cellulose acetate of the rare earth alloy of~7.8 molfractions and 1.1~2.2 molfractions.The system of the rare-earth type lithium iron phosphate
Preparation Method comprises the following steps：Fe source compound, Li source compound, P source compound and rare earth material are put into mixed powder machine to mix
Powder, progressively spray attachment in mixed powder, makes cellulose acetate uniformly glue to the cellulose acetate being dissolved in during mixed powder in acetone
On the mixture particle of four kinds of materials, then dry；Dried mixture particle is put into the gas of inert gas shielding
Atmosphere stove pre-burning；Powder after pre-burning is put into isothermal holding in the atmosphere furnace of inert gas shielding, rare-earth type lithium phosphoric acid is made
Iron lithium.
But there is after multiple circulation electric discharge the problem of loss of capacitance for above-mentioned lithium iron phosphate positive material.
The content of the invention
The purpose of the present invention is：A kind of LiFePO 4 material is provided, employ silane coupler grafting ionic liquid with
The electrostatic self-assembled principle of anion surfactant, the lithium iron phosphate positive material that material is evenly coated is prepared for, it is applied
When the positive electrode of lithium ion battery, there is the advantages of capacitance is big, discharging efficiency is high.
Technical scheme is：
The preparation method of lithium iron phosphate positive material, comprises the following steps：
1st step, by lithium hydroxide, 25~45 parts mix with 25~30 parts of water, 9~15 parts of ethanol, add silane coupler grafting
12~16 parts of ionic liquid be modified reaction；
2nd step, by ferric phosphate, 110~140 parts are formulated as the aqueous solution that solid content is 30~50wt.%, add ferric phosphate weight
2~4% anion surfactant, after mixed at high speed, be slowly added dropwise in the reactant that the 1st step obtains, stir, obtain
To slurry；
3rd step, slurry is obtained into LiFePO 4 material after being spray-dried, sintering.
In the 1st described step, range of reaction temperature is 15~35 DEG C；Reaction time is 1~3h.
In the 1st described step, the preparation method of the ionic liquid of silane coupler grafting is：In alcohols solvent, 1 is added
~5wt% silane coupler KH560 and 5~10% glyoxaline ion liquid, after reacting 10~20h at 80~100 DEG C, obtain
To the solution of the ionic liquid of silane coupler grafting.
Glyoxaline ion liquid be selected from chlorination -1- pi-allyl -3- methylimidazoles or chlorination 1- butyl -3- methylimidazoles or
One or more of mixing in person's imidazole radicals tetrafluoroborate ion liquid.
One or more of mixing of the described alcohols solvent in methanol, ethanol, propane diols, butanol or isoamyl alcohol.
Described anion surfactant is selected from fatty acid and their salt, such as oleic acid, palmitic acid, enuatrol, palm fibre
Palmitic acid acid potassium, and triethanolamine oleate；Hydroxyl institute's acids and their salt, such as hydroxyacetic acid, hydroxyacetic acid potassium, lactic acid and lactic acid
Potassium；More preferably hydroxyacetic acid.
In the 2nd described step, mixed at high speed refers to mix rotating speed in 1000~3000rpm.
In the 3rd described step, spray drying temperature is 140~210 DEG C；The condition of the sintering is in inert gas atmosphere
Lower progress, sintering temperature are 730~820 DEG C, and sintering time is 6~14h.
The lithium iron phosphate positive material being prepared by the above method.
Include the lithium ion battery of above-mentioned lithium iron phosphate positive material.
Beneficial effect
LiFePO 4 material provided by the invention, when it is applied to positive electrode of lithium ion battery, have that capacitance is big, electric discharge
The advantages of efficiency high, more circulation discharge time.
Embodiment
The present invention is described in further detail below by embodiment.But those skilled in the art will manage
Solution, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.Unreceipted specific skill in embodiment
Art or condition person, carried out according to the technology described by document in the art or condition or according to product description.Examination used
Agent or the unreceipted production firm person of instrument, being can be by the conventional products of acquisition purchased in market.
Word " comprising " used herein, "comprising", " having " or its any other variant are intended to cover non-exclusionism
Including.Technique, method, article or the equipment for e.g., including listing key element are not necessarily limited by those key elements, but can include
Other are not expressly set out or belonged to this technique, method, article or the intrinsic key element of equipment.
Scope is used as using what the value of range format expression should be interpreted as not only including clearly including in a flexible way
The numerical value of limit value, but also including covering all single numbers or subinterval within the range, just as each numerical value and sub-district
Between be expressly recited out.For example, " about 0.1% to about 5% " concentration range should be understood to not only include what is clearly included
The concentration of about 0.1% to about 5%, in addition to the single concentration in the range of alluding to（Such as, 1%, 2%, 3% and 4%）And subinterval（Example
Such as, 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%）.Percentage in the present invention refers to weight in the case of without specified otherwise
Percentage.
Lithium iron phosphate positive material preparation method provided by the present invention comprises the following steps：
1st step, by lithium hydroxide, 25~45 parts mix with 25~30 parts of water, 9~15 parts of ethanol, add silane coupler grafting
12~16 parts of ionic liquid be modified reaction；
2nd step, by ferric phosphate, 110~140 parts are formulated as the aqueous solution that solid content is 30~50wt.%, add ferric phosphate weight
2~4% anion surfactant, after mixed at high speed, be slowly added dropwise in the reactant that the 1st step obtains, stir, obtain
To slurry；
3rd step, slurry is obtained into LiFePO 4 material after being spray-dried, sintering.
Wherein, the ionic liquid being grafted first by lithium hydroxide and silane coupler reacts, and is grafted silane coupler
Ionic liquid cation modifying is carried out to lithium hydroxide slurry, then logical ferric phosphate is configured to containing anion surface active
The slurry of agent, after stirring, make the electrically charged property of particulate matter, the slurry that two steps are obtained carries out electrostatic self-assembled, real
The abundant absorption and mixing of existing material, the lithium iron phosphate positive material of sintering generation solid-state.
In 1st step, the preparation method of the ionic liquid of silane coupler grafting is：In alcohols solvent, 1~5wt% is added
Silane coupler KH560 and 5~10% glyoxaline ion liquid, at 80~100 DEG C react 10~20h after, obtain silane
The solution of the ionic liquid of coupling agent grafting.Glyoxaline ion liquid is selected from chlorination -1- pi-allyl -3- methylimidazoles or chlorination 1-
One or more of mixing in butyl -3- methylimidazoles or imidazole radicals tetrafluoroborate ion liquid.Described alcohols is molten
One or more of mixing of the agent in methanol, ethanol, propane diols, butanol or isoamyl alcohol.The effect of the step is hydroxide
Lithium slurry carries positive charge, after mixing, is more beneficial for making ferric phosphate be uniformly dispersed with lithium source.
In 2nd step, the purpose for adding anion surfactant is ferric phosphate slurry is carried negative electrical charge, above-mentioned steps
Middle suitable anion surfactant includes, for example, fatty acid and their salt, such as oleic acid, palmitic acid, enuatrol,
Potassium palmitate, and triethanolamine oleate；Hydroxyl institute's acids and their salt, such as hydroxyacetic acid, hydroxyacetic acid potassium, lactic acid and breast
Sour potassium；Polyoxyalkylene alkyl acetic acid class and their salt, such as the decyl ether acetic acid of polyoxyalkylene three and its sodium salt；Carboxyl-take more
The salt of the aromatic compounds in generation, such as trimellitic acid potassium and pyromellitic acid potassium；Benzene sulfonamide acids and their salt, such as dodecyl
Benzene sulfonic acid and its sodium salt；Polyoxyalkylene alkyl ethers sulfonic acid and their salt, such as polyethylene glycol oxide 2- ethylhexyls ether sulfonic acid and
Its sylvite；Higher fatty acid amides sulfonic acid and their salt, such as stearic acyl methyl taurine and its sodium salt, lauroyl methyl ox sulphur
Acid and its sodium salt, myristoyl methyl taurine and its sodium salt and PMT and its sodium salt；N- acyl group methyl amimoacetic acids
Class and their salt, such as Hamposyl L and its sodium salt；Alkyl phosphonic acid and their salt, such as octylphosphonate and its sylvite；
Aromatic phosphonic acids and their salt, such as phenyl phosphonic acid esters and its sylvite；Alkyl phosphonic acid phosphonate ester and their salt, such as 2- ethyls
Hexyl phosphonic acids list -2- ethylhexyls and its sylvite；Nitrogenous alkyl phosphonic acid and their salt, such as aminoethyl phosphonic acid and its diethanol
Amine salt；Alkyl sulfate and their salt, such as 2- ethyl hexyls sulfuric ester and its sodium salt；Polyoxyalkylene sulfuric acid ester and they
Salt, such as polyethylene glycol oxide 2- ethylhexyls ether sulfuric ester and its sodium salt；Alkyl phosphoric acid esters and their salt, such as base succinate
Class, such as two -2- ethylhexyls sodium sulfo-succinates and dioctyl sodium sulfosuccinate；And long-chain N- acyl glutamates, such as
The sodium of N- lauroyl glutamates one and N- stearoyls-Pidolidone disodium.For the consideration for improving battery capacity property, preferably adopt
Use oleic acid.
The material that 3rd step is so that reacts by high temperature sintering, and then generates the LiFePO 4 material of solid-state.
Heretofore described percentage is in the case of without special instruction all referring to mass percent.
Embodiment 1
The preparation method of positive electrode, comprises the following steps：
1st step, by lithium hydroxide, 25 parts mix with 25 parts of water, 9 parts of ethanol, add the ionic liquid of silane coupler grafting
12 parts of solution is modified reaction, and range of reaction temperature is 15 DEG C；Reaction time is 1h；The ionic liquid of silane coupler grafting
Preparation method be：In ethanol, 1wt% silane coupler KH560 and 5wt% chlorination -1- pi-allyl -3- methyl miaows are added
Oxazolinium ion liquid, after reacting 10h at 80 DEG C, obtain the solution of the ionic liquid of silane coupler grafting.
2nd step, by ferric phosphate, 110 parts are formulated as the aqueous solution that solid content is 30wt.%, add the 2% of ferric phosphate weight
Hydroxyacetic acid, speed of agitator is slowly added dropwise in the reactant that the 1st step obtains, stirs after 1000rpm mixed at high speed,
Obtain slurry；
3rd step, slurry is obtained into LiFePO 4 material after being spray-dried, sintering, spray drying temperature is 140 DEG C；It is described
The condition of sintering is carries out under inert gas atmosphere, and sintering temperature is 730 DEG C, sintering time 6h.
Embodiment 2
The preparation method of positive electrode, comprises the following steps：
1st step, by lithium hydroxide, 45 parts mix with 30 parts of water, 15 parts of ethanol, add the ionic liquid of silane coupler grafting
16 parts of solution be modified reaction, range of reaction temperature is 35 DEG C；Reaction time is 3h；The ionic liquid of silane coupler grafting
The preparation method of body is：In ethanol, 5wt% silane coupler KH560 and 10% chlorination -1- pi-allyl -3- methyl is added
Imidazole ion liquid, after reacting 20h at 100 DEG C, obtain the solution of the ionic liquid of silane coupler grafting.
2nd step, by ferric phosphate, 140 parts are formulated as the aqueous solution that solid content is 50wt.%, add the 4% of ferric phosphate weight
Hydroxyacetic acid, speed of agitator is slowly added dropwise in the reactant that the 1st step obtains, stirs after 3000rpm mixed at high speed,
Obtain slurry；
3rd step, slurry is obtained into LiFePO 4 material after being spray-dried, sintering, spray drying temperature is 210 DEG C；It is described
The condition of sintering is carries out under inert gas atmosphere, and sintering temperature is 820 DEG C, sintering time 14h.
Embodiment 3
The preparation method of positive electrode, comprises the following steps：
1st step, by lithium hydroxide, 30 parts mix with 28 parts of water, 12 parts of ethanol, add the ionic liquid of silane coupler grafting
13 parts of solution be modified reaction, range of reaction temperature is 20 DEG C；Reaction time is 2h；The ionic liquid of silane coupler grafting
The preparation method of body is：In ethanol, 2wt% silane coupler KH560 and 8% chlorination -1- pi-allyl -3- methyl miaows are added
Oxazolinium ion liquid, after reacting 15h at 90 DEG C, obtain the solution of the ionic liquid of silane coupler grafting.
2nd step, by ferric phosphate, 120 parts are formulated as the aqueous solution that solid content is 40wt.%, add the 3% of ferric phosphate weight
Hydroxyacetic acid, speed of agitator is slowly added dropwise in the reactant that the 1st step obtains, stirs after 2000rpm mixed at high speed,
Obtain slurry；
3rd step, slurry is obtained into LiFePO 4 material after being spray-dried, sintering, spray drying temperature is 170 DEG C；It is described
The condition of sintering is carries out under inert gas atmosphere, and sintering temperature is 750 DEG C, sintering time 10h.
Reference examples 1
Difference with embodiment 3 is：Ionic liquid solution is without silane coupler modified.
1st step, by lithium hydroxide, 30 parts mix with 28 parts of water, 12 parts of ethanol, and 13 parts of solution for adding ionic liquid enters
Row modified-reaction, range of reaction temperature are 20 DEG C；Reaction time is 2h；The preparation method of the solution of ionic liquid is：In ethanol
In, add 8% chlorination -1- pi-allyl -3- methylimidazole ionic liquids, stir.
2nd step, by ferric phosphate, 120 parts are formulated as the aqueous solution that solid content is 40wt.%, add the 3% of ferric phosphate weight
Hydroxyacetic acid, speed of agitator is slowly added dropwise in the reactant that the 1st step obtains, stirs after 2000rpm mixed at high speed,
Obtain slurry；
3rd step, slurry is obtained into LiFePO 4 material after being spray-dried, sintering, spray drying temperature is 170 DEG C；It is described
The condition of sintering is carries out under inert gas atmosphere, and sintering temperature is 750 DEG C, sintering time 10h.
Reference examples 2
Difference with embodiment 3 is：Anion surfactant hydroxyacetic acid is not added in the 2nd step.
The preparation method of positive electrode, comprises the following steps：
1st step, by lithium hydroxide, 30 parts mix with 28 parts of water, 12 parts of ethanol, add the ionic liquid of silane coupler grafting
13 parts of solution be modified reaction, range of reaction temperature is 20 DEG C；Reaction time is 2h；The ionic liquid of silane coupler grafting
The preparation method of body is：In ethanol, 2wt% silane coupler KH560 and 8% chlorination -1- pi-allyl -3- methyl miaows are added
Oxazolinium ion liquid, after reacting 15h at 90 DEG C, obtain the solution of the ionic liquid of silane coupler grafting.
2nd step, by ferric phosphate, 120 parts are formulated as the aqueous solution that solid content is 40wt.%, and speed of agitator is in 2000rpm high speeds
After mixing, it is slowly added dropwise in the reactant that the 1st step obtains, stirs, obtain slurry；
3rd step, slurry is obtained into LiFePO 4 material after being spray-dried, sintering, spray drying temperature is 170 DEG C；It is described
The condition of sintering is carries out under inert gas atmosphere, and sintering temperature is 750 DEG C, sintering time 10h.
Reference examples 3
Anions and canons codope lithium iron phosphate positive material in CN103441271A.
Reference examples 4
Lithium iron phosphate positive material in CN102569814A.
Test performance
1st, the preparation of battery is tested：
（1）The preparation of positive plate：, will using LiFePO 4 material prepared by embodiment and reference examples as positive electrode active materials
Positive electrode, acetylene black and PVDF are using weight ratio as 100：4：5 are dissolved in 1-METHYLPYRROLIDONE, and aluminium is coated in after stirring
On paper tinsel, baking, temperature is 100 ± 5 DEG C, is rolled by certain thickness using tablet press machine, and rolling cut is into positive plate；
（2）The preparation of negative plate：By graphite, acetylene black and PVDF using weight ratio as 100：3：6 are dissolved in 1-METHYLPYRROLIDONE,
Coated on copper foil after stirring, baking, temperature is 100 ± 5 DEG C, is rolled by certain thickness using tablet press machine, rolling cut into
Negative plate；
（3）Above-mentioned positive and negative plate and polypropylene diaphragm are wound into rectangular lithium ion battery battery core, is placed in battery case and goes forward side by side
Row welding, it is subsequently injected into 1.0mol/L LiPF6(wherein, EC, EMC and DMC mass ratio are 1 to/EC+EMC+DMC：1：1) it is electrolysed
Liquid, sealing, is made test battery.
2.1st, specific capacity is tested：
At room temperature, test battery is shelved into 5min, first with 0.8mA constant-current charges, by voltage 3.8V, filled in 3.8V constant pressures
Electricity, by electric current 0.1mA, 5min is shelved, with 0.8mA constant-current discharges, limitation voltage 2.5V.Its specific capacity is calculated, is as a result seen below
Table.
2.2nd, cycle performance is tested
At room temperature, will test battery first with 0.8mA constant-current charges, voltage 3.8V is limited, in 3.8V constant-voltage charges, by electric current
0.1mA, 5min is shelved, with 0.8mA constant-current discharges.Repeat 500 times, calculate 500 capability retentions, as a result see the table below.
| 2.5~3.8V specific capacities 1 (mAh/g) | 2.5~3.8V specific capacities 2 (mAh/g) | 2.5~3.8V specific capacities 3 (mAh/g) | 200 capability retentions (%) | Discharging efficiency (%) | |
| Embodiment 1 | 166 | 167 | 168 | 96.5 | 98 |
| Embodiment 2 | 167 | 166 | 168 | 96.2 | 97 |
| Embodiment 3 | 168 | 167 | 169 | 97.5 | 99 |
| Reference examples 1 | 152 | 151 | 153 | 93.5 | 96 |
| Reference examples 2 | 150 | 152 | 152 | 92.8 | 95 |
| Reference examples 3 | 156 | 157 | 157 | 93.6 | 95 |
| Reference examples 4 | 152 | 153 | 152 | 92.4 | 94 |
The specific capacity that LiFePO 4 material made from the preparation method of the embodiment of the present invention makes is big, and has longer circulation
Discharge life；Embodiment 3 is ion liquid modified by being carried out to lithium hydroxide slurry for reference examples 1, can be effective
Ground makes preferably to mix by electrostatic self-assembled realization between material, and there is the positive electrode being prepared higher circulation to discharge
Electricity retentivity；And embodiment 3 is relative to reference examples 2, by using anion surfactant to ferric phosphate slurry agitation at
Reason, the electronegativity of slurry can be improved, be advantageous to the process of electrostatic self-assembled.After 200 circulation electric discharges of above-mentioned material
Capability retention is better than positive electrode of the prior art.
Claims (10)
1. a kind of preparation method of lithium iron phosphate positive material, it is characterised in that comprise the following steps：
1st step, by lithium hydroxide, 25~45 parts mix with 25~30 parts of water, 9~15 parts of ethanol, add silane coupler grafting
12~16 parts of ionic liquid be modified reaction；
2nd step, by ferric phosphate, 110~140 parts are formulated as the aqueous solution that solid content is 30~50wt.%, add ferric phosphate weight
2~4% anion surfactant, after mixed at high speed, be slowly added dropwise in the reactant that the 1st step obtains, stir, obtain
To slurry；
3rd step, slurry is obtained into LiFePO 4 material after being spray-dried, sintering.
2. the preparation method of lithium iron phosphate positive material according to claim 1, it is characterised in that in the 1st described step,
Range of reaction temperature is 15~35 DEG C；Reaction time is 1~3h.
3. the preparation method of lithium iron phosphate positive material according to claim 1, it is characterised in that in the 1st described step,
The preparation method of ionic liquid of silane coupler grafting is：In alcohols solvent, 1~5wt% silane coupler is added
KH560 and 5~10% glyoxaline ion liquid, after reacting 10~20h at 80~100 DEG C, obtain silane coupler grafting
The solution of ionic liquid.
4. the preparation method of lithium iron phosphate positive material according to claim 1, it is characterised in that glyoxaline ion liquid
Selected from chlorination -1- pi-allyl -3- methylimidazoles or chlorination 1- butyl -3- methylimidazoles or imidazole radicals tetrafluoro boric acid salt ion
One or more of mixing in liquid.
5. the preparation method of lithium iron phosphate positive material according to claim 1, it is characterised in that described alcohols solvent
One or more of mixing in methanol, ethanol, propane diols, butanol or isoamyl alcohol.
6. the preparation method of lithium iron phosphate positive material according to claim 1, it is characterised in that described anion table
Face activating agent is selected from fatty acid and their salt, such as oleic acid, palmitic acid, enuatrol, potassium palmitate, and triethanolamine oleate；
Hydroxyl institute's acids and their salt, such as hydroxyacetic acid, hydroxyacetic acid potassium, lactic acid and potassium lactate；More preferably hydroxyacetic acid.
7. the preparation method of lithium iron phosphate positive material according to claim 1, it is characterised in that in the 2nd described step,
Mixed at high speed refers to mix rotating speed in 1000~3000rpm.
8. the preparation method of lithium iron phosphate positive material according to claim 1, it is characterised in that in the 3rd described step,
Spray drying temperature is 140~210 DEG C；The condition of the sintering to carry out under inert gas atmosphere, sintering temperature is 730~
820 DEG C, sintering time is 6~14h.
9. the LiFePO4 that the preparation method of the lithium iron phosphate positive material described in any one of claim 1~8 is directly obtained
Positive electrode.
10. include the lithium ion battery of the lithium iron phosphate positive material described in claim 9.
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