CN106207169B - A kind of preparation method of carbon gel coated LiFePO 4 for lithium ion batteries positive electrode - Google Patents

A kind of preparation method of carbon gel coated LiFePO 4 for lithium ion batteries positive electrode Download PDF

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CN106207169B
CN106207169B CN201610636120.XA CN201610636120A CN106207169B CN 106207169 B CN106207169 B CN 106207169B CN 201610636120 A CN201610636120 A CN 201610636120A CN 106207169 B CN106207169 B CN 106207169B
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flask
lithium ion
carbon gel
positive electrode
ion batteries
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CN106207169A (en
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张国华
盛海丰
王统军
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Zhou Zhicai
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621Binders
    • H01M4/622Binders being polymers
    • H01M4/623Binders being polymers fluorinated polymers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection 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
    • H01M4/5825Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621Binders
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a kind of preparation methods of carbon gel coated LiFePO 4 for lithium ion batteries positive electrode, belong to lithium iron phosphate positive material preparation technical field.The present invention is prepared into graphite oxide using graphite; restore to obtain graphene; and it is dispersed in distilled water and obtains graphene dispersing solution; the carbon gel that aging in reaction kettle obtains doped graphene is added in itself and resorcinol, formaldehyde; and the lysate of LiFePO4 raw material is added into reaction kettle, it reacts under nitrogen protection, obtains reactant; and it calcines at different temperatures respectively, the method for obtaining carbon gel coated LiFePO 4 for lithium ion batteries positive electrode.The beneficial effects of the present invention are: products obtained therefrom conductivity of the present invention is high, specific capacity reaches 205mAh/g or more, low temperature performance well;Using carbon gel coated LiFePO 4 for lithium ion batteries positive electrode, solve that tap density is lower, electrode ion spreads slow problem, and tap density is greater than 1.6 × 10 up to 1.8~2.3g/mL, the diffusion coefficient of electrode ion‑12cm2/s。

Description

A kind of preparation method of carbon gel coated LiFePO 4 for lithium ion batteries positive electrode
Technical field
The present invention relates to a kind of preparation methods of carbon gel coated LiFePO 4 for lithium ion batteries positive electrode, belong to iron phosphate lithium positive pole material Expect preparation technical field.
Background technique
In recent years, as resource scarcity, problem of environmental pollution become increasingly conspicuous, new energy is especially with lithium ion battery The energy energy storage device of representative rapidly develops, and constantly replaces ni-Cd, nickel in fields such as electric car, medical instrument and communication apparatus The traditional storage batteries such as hydrogen.LiFePO4 because it has many advantages, such as be considered as can replace cobalt acid lithium become next-generation lithium from The first choice of sub- cell positive material.But LiFePO4 itself has complicated preparation process, poorly conductive and lithium ion diffusion slow The disadvantages of.Lithium iron phosphate electrode material is mainly used for various lithium ion batteries.The service life of ferric phosphate lithium cell is used with it Temperature is closely bound up, generates very big bad hidden danger in its charge and discharge process and use process using temperature is too low or too high. Especially used on north of China electric car, autumn and winter ferric phosphate lithium cell can not normal power supply or power supply it is too low, Its operating ambient temperature need to be adjusted and keep its performance.Big multiplying power charging can be used, most in the lithium battery of lithium iron phosphate positive material Battery can be full of in 1 hour fastly.But poorly conductive, tap density are lower.Generally it can only achieve 1.3~1.5g/ml, it is low Tap density can be described as the disadvantage of LiFePO4.Using coated modified carbon to lithium iron phosphate positive material in electric conductivity Difference, lithium ion spread slow etc. deficiency and are significantly improved.Simple conductive layer cladding means, can only improve material surface Electron conduction, electron conduction and ion diffusion rates for LiFePO4 crystals do not influence but, thus right It is limited in the promotion of LiFePO 4 material chemical property.Carbon coating layer limit ferric phosphate crystalline lithium growth, shorten lithium from Diffusion length of the son in crystal, causes material electric conductivity low, and poor performance at low temperatures, tap density is lower, and electrode ion diffusion is slow.
Summary of the invention
The technical problems to be solved by the invention: iron phosphate lithium positive pole material is prepared for simple conductive layer cladding process Material limits the growth of ferric phosphate crystalline lithium, shortens diffusion length of the lithium ion in crystal, cause material electric conductivity low, low Warm nature can it is poor, tap density is lower, and electrode ion spreads slow drawback, provide it is a kind of utilization graphite oxidation stone is prepared Ink restores to obtain graphene, and is dispersed in distilled water and obtains graphene dispersing solution, by itself and resorcinol, formaldehyde addition reaction kettle Middle aging obtains the carbon gel of doped graphene, and the lysate of Fe (NO3) 3, NH4H2PO4, LiNO3 are added into reaction kettle, It is reacted under nitrogen protection, obtains reactant, and calcined at different temperatures respectively, obtain carbon gel coated LiFePO 4 for lithium ion batteries positive electrode Method.Preparation step of the present invention is simple, and products obtained therefrom conductivity is high, and low temperature performance well makes full use of carbon gel cladding to prepare phosphorus Sour iron lithium anode material, efficiently solves that material tap density is lower, and electrode ion spreads slow problem.
In order to solve the above technical problems, the present invention is using technical solution as described below:
(1) it weighs 4~6g graphite powder to be put into three-necked flask, flask is put into 0~5 DEG C of ice bath pot, the side into flask The mixed acid of 200~300mL is slowly added dropwise in stirring side, and control rate of addition is 5~10mL/min, after completion of dropwise addition, adds 20~30g potassium permanganate after being stirred 20~30min, flask is moved into water-bath, is stirred to react 12 at 55~60 DEG C ~18h increases bath temperature to 98 DEG C again after reaction, and insulated and stirred reacts 10~15min;The mixed acid is quality 10:1 is mixed by volume for 98% sulfuric acid of score and 80% phosphoric acid of mass fraction;
(2) above-mentioned that flask is taken out from water-bath after reaction, and 6~8mL mass fraction 30% is added into flask Hydrogen peroxide, stirring filters to obtain filter residue, respectively with 5% hydrochloric acid of mass fraction and deionized water to its ultrasound until bubble-free generates 5~10min is cleaned, then is centrifugated to obtain sediment, ground after freeze-drying, cross 100~120 meshes, obtain the fluffy oxygen of structure Graphite powder, graphite oxide powder is placed on the quartz boat of tube furnace, is heated to 300~500 DEG C under protection of argon gas, also Original 1~2h of reaction, obtains graphene, by solid-to-liquid ratio 1:10, graphene is mixed with distilled water, 10~15min of ultrasonic disperse obtains stone Black alkene dispersion liquid;
(3) 1.5~2.0g resorcinol, 3~5mL formaldehyde and the above-mentioned graphene dispersing solution of 35~40mL are weighed respectively, are used It is 7.0 that sodium bicarbonate, which adjusts pH, stainless steel autoclave is poured into after adjusting, aging 3~4 days at 60~70 DEG C;
(4) after to be aging, 1:1:1, weighs 4.82gFe (NO respectively in molar ratio3)3、2.30gNH4H2PO4、 1.38gLiNO3In beaker, and 15~20mL distilled water is added, stirring is completely dissolved to solid, by lysate be added it is above-mentioned not It becomes rusty in steel autoclave, nitrogen is led into reaction kettle, under nitrogen protection, be warming up to 80~100 DEG C, keep the temperature 1~2h, heat preservation 180~220 DEG C are warming up to 5~10 DEG C/min rate afterwards, 8~10h is reacted, filters after reaction, obtain filter residue, by filter residue point It Yong not be put into vacuum oven, dry 5~6h at 50~60 DEG C after dehydrated alcohol and water rinses;
(5) solid after above-mentioned drying is packed into porcelain boat, porcelain boat is put into tube furnace, in a nitrogen atmosphere, with 5~8 DEG C/min rate program is warming up to 200~300 DEG C of 2~3h of calcining, then is warming up to 400~500 DEG C of 2~3h of calcining, then heat up To 600~700 DEG C of 3~4h of calcining, room temperature is cooled to after calcining to get carbon gel coated LiFePO 4 for lithium ion batteries positive electrode.
Application method of the invention: the carbon gel coated LiFePO 4 for lithium ion batteries positive electrode for taking 48~55mg to prepare, addition 6~ 7mg polytetrafluoroethylene (PTFE) and 7~9mg acetylene black, stirring are allowed to uniformly mixed, diameter 4~6mm pole piece are pressed into, 100~105 Dry 8~12h, is subsequently placed into glove box and encapsulates battery at DEG C, stands 12~15h.The material tap density up to 1.8~ 2.3g/mL, conductivity is high, and specific capacity reaches 205mAh/g or more, diffusion coefficient >=1.6 × 10 of electrode ion-12cm2/ s, low temperature Performance is good, is worthy to be popularized and uses.
The present invention is compared with other methods, and advantageous effects are:
(1) preparation step of the present invention is simple, and products obtained therefrom conductivity is high, and specific capacity reaches 205mAh/g or more, cryogenic property It is good;
(2) porous carbon materials of the carbon gel as a kind of rule have continuous, high conductivity of structure etc. better than other carbon materials The performance of material can substitute traditional simple graphite carbon encapsulated material;
(3) carbon gel cladding is made full use of to prepare lithium iron phosphate positive material, it is lower to efficiently solve material tap density, Electrode ion spreads slow problem, and tap density is up to 1.8~2.3g/mL, diffusion coefficient >=1.6 × 10 of electrode ion-12cm2/ s。
Specific embodiment
4~6g graphite powder is weighed first to be put into three-necked flask, flask is put into 0~5 DEG C of ice bath pot, the side into flask The mixed acid of 200~300mL is slowly added dropwise in stirring side, and control rate of addition is 5~10mL/min, after completion of dropwise addition, adds 20~30g potassium permanganate after being stirred 20~30min, flask is moved into water-bath, is stirred to react 12 at 55~60 DEG C ~18h increases bath temperature to 98 DEG C again after reaction, and insulated and stirred reacts 10~15min;The mixed acid is quality 10:1 is mixed by volume for 98% sulfuric acid of score and 80% phosphoric acid of mass fraction;It is above-mentioned after reaction, taken from water-bath Flask out, and into flask be added 6~8mL mass fraction 30% hydrogen peroxide, stirring until bubble-free generate, filter to obtain filter residue, It is cleaned by ultrasonic 5~10min to it with 5% hydrochloric acid of mass fraction and deionized water respectively, then is centrifugated to obtain sediment, freezing is dry It ground after dry, cross 100~120 meshes, obtained the fluffy graphite oxide powder of structure, graphite oxide powder is placed in the stone of tube furnace On Ying Zhou, it is heated to 300~500 DEG C under protection of argon gas, 1~2h of reduction reaction obtains graphene, by solid-to-liquid ratio 1:10, by stone Black alkene is mixed with distilled water, and 10~15min of ultrasonic disperse obtains graphene dispersing solution;Weigh 1.5~2.0g isophthalic two respectively again Phenol, 3~5mL formaldehyde and the above-mentioned graphene dispersing solution of 35~40mL, adjusting pH with sodium bicarbonate is 7.0, is poured into after adjusting stainless Steel autoclave, aging 3~4 days at 60~70 DEG C;After to be aging, 1:1:1, weighs respectively in molar ratio 4.82gFe(NO3)3、2.30gNH4H2PO4、1.38gLiNO3In beaker, and 15~20mL distilled water is added, stirring to solid It is completely dissolved, lysate is added in above-mentioned stainless steel autoclave, nitrogen is led into reaction kettle, under nitrogen protection, rise Temperature keeps the temperature 1~2h to 80~100 DEG C, is warming up to 180~220 DEG C after heat preservation with 5~10 DEG C/min rate, reacts 8~10h, instead It is filtered after answering, obtains filter residue, after filter residue being used respectively dehydrated alcohol and water rinse, be put into vacuum oven, 50~60 Dry 5~6h at DEG C;The solid after above-mentioned drying is finally packed into porcelain boat, porcelain boat is put into tube furnace, in a nitrogen atmosphere, 200~300 DEG C of 2~3h of calcining are warming up to 5~8 DEG C/min rate program, then are warming up to 400~500 DEG C of 2~3h of calcining, with After be warming up to 600~700 DEG C of 3~4h of calcining, room temperature is cooled to after calcining to get carbon gel coated LiFePO 4 for lithium ion batteries anode material Material.
Example 1
4g graphite powder is weighed first to be put into three-necked flask, flask is put into 0 DEG C of ice bath pot, while stirring into flask The mixed acid of 200mL is slowly added dropwise, control rate of addition is 5mL/min, after completion of dropwise addition, adds 20g potassium permanganate, is stirred After mixing 20min, flask is moved into water-bath, 12h is stirred to react at 55 DEG C, increases bath temperature again extremely after reaction 98 DEG C, insulated and stirred reacts 10min;The mixed acid be 98% sulfuric acid of mass fraction and 80% phosphoric acid of mass fraction by volume 10:1 is mixed;It is above-mentioned that flask is taken out from water-bath after reaction, and 6mL mass fraction 30% is added into flask Hydrogen peroxide, stirring filter to obtain filter residue until bubble-free generation, clear to its ultrasound with 5% hydrochloric acid of mass fraction and deionized water respectively 5min is washed, then is centrifugated to obtain sediment, grinds, sieve with 100 mesh sieve after freeze-drying, obtains the fluffy graphite oxide powder of structure, Graphite oxide powder is placed on the quartz boat of tube furnace, is heated to 300 DEG C under protection of argon gas, reduction reaction 1h obtains graphite Alkene is mixed graphene with distilled water by solid-to-liquid ratio 1:10, and ultrasonic disperse 10min obtains graphene dispersing solution;It weighs respectively again 1.5g resorcinol, 3mL formaldehyde and the above-mentioned graphene dispersing solution of 35mL, adjusting pH with sodium bicarbonate is 7.0, is poured into not after adjusting Become rusty steel autoclave, aging 3 days at 60 DEG C;After to be aging, 1:1:1, weighs 4.82gFe respectively in molar ratio (NO3)3、2.30gNH4H2PO4、1.38gLiNO3In beaker, and 15mL distilled water is added, stirring to solid is completely dissolved, will Lysate is added in above-mentioned stainless steel autoclave, and nitrogen is led into reaction kettle, under nitrogen protection, is warming up to 80 DEG C, protects Warm 1h is warming up to 180 DEG C after heat preservation with 5 DEG C/min rate, reacts 8h, filters after reaction, obtain filter residue, filter residue is used respectively It after dehydrated alcohol and water rinse, is put into vacuum oven, the dry 5h at 50 DEG C;Finally the solid after above-mentioned drying is packed into Porcelain boat is put into tube furnace by porcelain boat, in a nitrogen atmosphere, is warming up to 200 DEG C of calcining 2h with 5 DEG C/min rate program, then rise Temperature then raises temperature to 600 DEG C of calcining 3h, room temperature is cooled to after calcining to get carbon gel and coats phosphoric acid to 400 DEG C of calcining 2h Iron lithium anode material.
6mg polytetrafluoroethylene (PTFE) and 7mg acetylene black is added in the carbon gel coated LiFePO 4 for lithium ion batteries positive electrode for taking 48mg to prepare, Stirring is allowed to uniformly mixed, is pressed into diameter 4mm pole piece, and dry 8h, is subsequently placed into glove box and encapsulates battery at 100 DEG C, Stand 12h.The material tap density reaches 1.8g/mL, and conductivity is high, and specific capacity reaches 209mAh/g, the diffusion of electrode ion Coefficient is 1.6 × 10-12cm2/ s, low temperature performance well are worthy to be popularized and use.
Example 2
5g graphite powder is weighed first to be put into three-necked flask, flask is put into 3 DEG C of ice bath pots, while stirring into flask The mixed acid of 250mL is slowly added dropwise, control rate of addition is 8mL/min, after completion of dropwise addition, adds 25g potassium permanganate, is stirred After mixing 25min, flask is moved into water-bath, 15h is stirred to react at 58 DEG C, increases bath temperature again extremely after reaction 98 DEG C, insulated and stirred reacts 13min;The mixed acid be 98% sulfuric acid of mass fraction and 80% phosphoric acid of mass fraction by volume 10:1 is mixed;It is above-mentioned that flask is taken out from water-bath after reaction, and 7mL mass fraction 30% is added into flask Hydrogen peroxide, stirring filter to obtain filter residue until bubble-free generation, clear to its ultrasound with 5% hydrochloric acid of mass fraction and deionized water respectively 8min is washed, then is centrifugated to obtain sediment, ground after freeze-drying, cross 110 meshes, obtain the fluffy graphite oxide powder of structure, Graphite oxide powder is placed on the quartz boat of tube furnace, is heated to 400 DEG C under protection of argon gas, reduction reaction 2h obtains graphite Alkene is mixed graphene with distilled water by solid-to-liquid ratio 1:10, and ultrasonic disperse 13min obtains graphene dispersing solution;It weighs respectively again 1.8g resorcinol, 4mL formaldehyde and the above-mentioned graphene dispersing solution of 38mL, adjusting pH with sodium bicarbonate is 7.0, is poured into not after adjusting Become rusty steel autoclave, aging 4 days at 65 DEG C;After to be aging, 1:1:1, weighs 4.82gFe respectively in molar ratio (NO3)3、2.30gNH4H2PO4、1.38gLiNO3In beaker, and 18mL distilled water is added, stirring to solid is completely dissolved, will Lysate is added in above-mentioned stainless steel autoclave, and nitrogen is led into reaction kettle, under nitrogen protection, is warming up to 90 DEG C, protects Warm 2h is warming up to 200 DEG C after heat preservation with 8 DEG C/min rate, reacts 9h, filters after reaction, obtain filter residue, filter residue is used respectively It after dehydrated alcohol and water rinse, is put into vacuum oven, the dry 6h at 55 DEG C;Finally the solid after above-mentioned drying is packed into Porcelain boat is put into tube furnace by porcelain boat, in a nitrogen atmosphere, is warming up to 250 DEG C of calcining 3h with 7 DEG C/min rate program, then rise Temperature then raises temperature to 650 DEG C of calcining 4h, room temperature is cooled to after calcining to get carbon gel and coats phosphoric acid to 450 DEG C of calcining 3h Iron lithium anode material.
7mg polytetrafluoroethylene (PTFE) and 8mg acetylene black is added in the carbon gel coated LiFePO 4 for lithium ion batteries positive electrode for taking 51mg to prepare, Stirring is allowed to uniformly mixed, is pressed into diameter 5mm pole piece, and dry 10h, is subsequently placed into glove box and encapsulates battery at 103 DEG C, Stand 14h.The material tap density reaches 2.1g/mL, and conductivity is high, and specific capacity reaches 216mAh/g, the diffusion of electrode ion Coefficient is 1.7 × 10-12cm2/ s, low temperature performance well are worthy to be popularized and use.
Example 3
6g graphite powder is weighed first to be put into three-necked flask, flask is put into 5 DEG C of ice bath pots, while stirring into flask The mixed acid of 300mL is slowly added dropwise, control rate of addition is 10mL/min, after completion of dropwise addition, adds 30g potassium permanganate, stirs After mixing mixing 30min, flask is moved into water-bath, 18h is stirred to react at 60 DEG C, increases bath temperature again after reaction To 98 DEG C, insulated and stirred reacts 15min;The mixed acid is 98% sulfuric acid of mass fraction and 80% phosphoric acid of mass fraction by volume It is mixed than 10:1;It is above-mentioned that flask is taken out from water-bath after reaction, and 8mL mass fraction 30% is added into flask Hydrogen peroxide, stirring filters to obtain filter residue, respectively with 5% hydrochloric acid of mass fraction and deionized water to its ultrasound until bubble-free generates 10min is cleaned, then is centrifugated to obtain sediment, ground after freeze-drying, cross 120 meshes, obtain the fluffy graphite oxide powder of structure End, graphite oxide powder is placed on the quartz boat of tube furnace, is heated to 500 DEG C under protection of argon gas, and reduction reaction 2h obtains stone Black alkene is mixed graphene with distilled water by solid-to-liquid ratio 1:10, and ultrasonic disperse 15min obtains graphene dispersing solution;Claim respectively again 2.0g resorcinol, 5mL formaldehyde and the above-mentioned graphene dispersing solution of 40mL are taken, adjusting pH with sodium bicarbonate is 7.0, is poured into after adjusting Stainless steel autoclave, aging 4 days at 70 DEG C;After to be aging, 1:1:1, weighs 4.82gFe respectively in molar ratio (NO3)3、2.30gNH4H2PO4、1.38gLiNO3In beaker, and 20mL distilled water is added, stirring to solid is completely dissolved, will Lysate is added in above-mentioned stainless steel autoclave, and nitrogen is led into reaction kettle, under nitrogen protection, is warming up to 100 DEG C, protects Warm 2h is warming up to 220 DEG C after heat preservation with 10 DEG C/min rate, reacts 10h, filters after reaction, obtain filter residue, filter residue is distinguished It after being rinsed with dehydrated alcohol and water, is put into vacuum oven, the dry 6h at 60 DEG C;Finally the solid after above-mentioned drying is filled Enter porcelain boat, porcelain boat is put into tube furnace, in a nitrogen atmosphere, 300 DEG C of calcining 3h is warming up to 8 DEG C/min rate program, then 500 DEG C of calcining 3h are warming up to, 700 DEG C of calcining 4h are then raised temperature to, room temperature is cooled to after calcining to get carbon gel and coats phosphorus Sour iron lithium anode material.
7mg polytetrafluoroethylene (PTFE) and 9mg acetylene black is added in the carbon gel coated LiFePO 4 for lithium ion batteries positive electrode for taking 55mg to prepare, Stirring is allowed to uniformly mixed, is pressed into diameter 6mm pole piece, and dry 12h, is subsequently placed into glove box and encapsulates battery at 105 DEG C, Stand 15h.The material tap density reaches 2.3g/mL, and conductivity is high, and specific capacity reaches 235mAh/g, the diffusion of electrode ion Coefficient is 1.8 × 10-12cm2/ s, low temperature performance well are worthy to be popularized and use.

Claims (1)

1. a kind of preparation method of carbon gel coated LiFePO 4 for lithium ion batteries positive electrode, it is characterised in that specific preparation step are as follows:
(1) it weighs 4~6g graphite powder to be put into three-necked flask, flask is put into 0~5 DEG C of ice bath pot, side is stirred into flask While the mixed acid of 200~300mL is slowly added dropwise, control rate of addition is 5~10mL/min, after completion of dropwise addition, add 20~ After being stirred 20~30min, flask is moved into water-bath for 30g potassium permanganate, it is stirred to react 12 at 55~60 DEG C~ 18h increases bath temperature to 98 DEG C again after reaction, and insulated and stirred reacts 10~15min;The mixed acid is quality point 10:1 is mixed by volume for several 98% sulfuric acid and 80% phosphoric acid of mass fraction;
(2) above-mentioned that flask is taken out from water-bath after reaction, and the double of 6~8mL mass fraction 30% are added into flask Oxygen water, stirring are filtered to obtain filter residue, are cleaned by ultrasonic respectively with 5% hydrochloric acid of mass fraction and deionized water to it until bubble-free generation 5~10min, then it is centrifugated to obtain sediment, it ground after freeze-drying, cross 100~120 meshes, obtain the fluffy oxidation stone of structure Ink powder end, graphite oxide powder is placed on the quartz boat of tube furnace, is heated to 300~500 DEG C under protection of argon gas, reduction is anti- 1~2h is answered, graphene is obtained, by solid-to-liquid ratio 1:10, graphene is mixed with distilled water, 10~15min of ultrasonic disperse obtains graphene Dispersion liquid;
(3) 1.5~2.0g resorcinol, 3~5mL formaldehyde and the above-mentioned graphene dispersing solution of 35~40mL are weighed respectively, use carbonic acid It is 7.0 that hydrogen sodium, which adjusts pH, stainless steel autoclave is poured into after adjusting, aging 3~4 days at 60~70 DEG C;
(4) after to be aging, 1:1:1, weighs 4.82gFe (NO respectively in molar ratio3)3、2.30gNH4H2PO4、 1.38gLiNO3In beaker, and 15~20mL distilled water is added, stirring is completely dissolved to solid, by lysate be added it is above-mentioned not It becomes rusty in steel autoclave, nitrogen is led into reaction kettle, under nitrogen protection, be warming up to 80~100 DEG C, keep the temperature 1~2h, heat preservation 180~220 DEG C are warming up to 5~10 DEG C/min rate afterwards, 8~10h is reacted, filters after reaction, obtain filter residue, by filter residue point It Yong not be put into vacuum oven, dry 5~6h at 50~60 DEG C after dehydrated alcohol and water rinses;
(5) by after above-mentioned drying solid be packed into porcelain boat, porcelain boat is put into tube furnace, in a nitrogen atmosphere, with 5~8 DEG C/ Min rate program is warming up to 200~300 DEG C of 2~3h of calcining, then is warming up to 400~500 DEG C of 2~3h of calcining, then raises temperature to 600~700 DEG C of 3~4h of calcining are cooled to room temperature to get carbon gel coated LiFePO 4 for lithium ion batteries positive electrode after calcining.
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CN108565409B (en) * 2018-01-19 2020-06-09 河北力滔电池材料有限公司 Lithium iron phosphate composite material and preparation method thereof
CN109004207B (en) * 2018-06-29 2021-06-25 武汉船用电力推进装置研究所(中国船舶重工集团公司第七一二研究所) Composite lithium iron phosphate cathode material and preparation method thereof
CN108899506A (en) * 2018-07-03 2018-11-27 广州大学 A kind of porous nano carbon coating manganate cathode material for lithium and preparation method thereof
CN114122406B (en) * 2022-01-25 2022-11-08 成都特隆美储能技术有限公司 Preparation method of graphene modified lithium iron phosphate and lithium iron phosphate

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