CN103872287A - Composite positive electrode material of graphene and lithium iron phosphate battery and preparation method thereof - Google Patents
Composite positive electrode material of graphene and lithium iron phosphate battery and preparation method thereof Download PDFInfo
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- CN103872287A CN103872287A CN201410105044.0A CN201410105044A CN103872287A CN 103872287 A CN103872287 A CN 103872287A CN 201410105044 A CN201410105044 A CN 201410105044A CN 103872287 A CN103872287 A CN 103872287A
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention discloses a composite positive electrode material of a graphene and lithium iron phosphate battery and a preparation method thereof. The composite positive electrode material of the graphene and lithium iron phosphate battery is composed of graphene and a LiFePO4 lithium ion battery positive electrode material in the mass percentage range of 0.1%-8%. The composite material sufficiently utilizes the good conductive performance of the graphene so that the electronic conductivity and the discharging rate capability of the positive electrode material of the lithium iron phosphate ion battery are improved; a graphene filling process is simple and the price is low.
Description
Technical field
The invention belongs to lithium ion battery manufacture technology field, relate to a kind of Graphene lithium iron phosphate battery anode composite material and preparation method thereof.
Background technology
Lithium ion battery, as a kind of novel secondary cell, has the advantages that specific capacity is high, voltage is high, fail safe is good, and the main component of lithium ion battery is LiFePO4 (LiFePO
4), lithium ion deviate from telescopiny in without change in volume, under high temperature, do not discharge active oxygen, there is good charge-discharge cycle and fail safe, being widely used in the driving power of electric automobile, mobile phone, notebook computer, is also the main component of electric automobile power battery research.LiFePO at present
4process of industrialization run into some difficulties, specifically comprise: 1. LiFePO
4conductivity low, be only suitable for discharging under low current density.2. ferrous ion is easily oxidized, in synthesizing, needs strict control, and technical difficulty is higher.3. need to reduce LiFePO
4particle diameter shortens lithium ion the evolving path, but this point reaches industrial being difficult to.4. the tap density that improves product is very difficult, LiFePO
4mainly by high temperature solid-state method, coprecipitation, hydro thermal method, the method preparations such as sol-gal process and microwave method, the LiFePO preparing in experiment
4have crystal boundary, and lithium ion has obvious decline in grain boundaries migration rate, simultaneously LiFePO
4the conductivity of material itself is also lower, and these 2 factors all can greatly affect the performance of lithium ion battery, in order to address this problem, normally at LiFePO
4the coated layer of conductive material in surface, the people such as Ellis improve LiFePO by coated agraphitic carbon between solid interface
4conductivity, but the method be by high temperature pyrolysis of organic substance produce carbon be coated on LiFePO
4surface, therefore cannot guarantee the integrality that carbon is coated, to LiFePO
4the raising of conductivity limited, research is at present found when using titanium dioxide rubidium (RuO
2) be filled in the space of coated carbon-coating after, LiFePO
4charge-discharge performance be significantly increased, but RuO
2expensive, and experiment condition complexity, be unfavorable for practical application.After thering is the Graphene (graphite) of plumbago single slice layer structure and being found in 2004, constantly there is the report about its superior mechanical performance and superelevation conductance, Graphene is the material with carbon element by individual layer or the two-dimentional hexagonal lattice structure of the tightly packed one-tenth of which floor carbon atom, be the current the highest material of known strength in the world, its electric property is also best in current material.Therefore can be at LiFePO
4in material, participating in appropriate is Graphene, to LiFePO
4the inherent defect of material improves, and improves the each side chemical property of Graphene, prepares at present Graphene and mainly contains mechanical glass method, and silicon carbide epitaxy is thought of a way, chemical vapour deposition technique and graphene oxide reducing process.
The LiFePO of olivine structural
4because of its compared with height ratio capacity, the anode material for lithium-ion batteries of new generation of advantage the becomes tool development and application potentiality such as environmentally friendly, cycle performance is desirable, security performance is good, with low cost.Then, low lithium ion diffusion coefficient and electronic conductivity, make LiFePO
4in the time of high rate charge-discharge, specific capacity declines rapidly, and hindered, it is further practical.Traditional method of modifying carbon is coated can reduce anodal volume energy density of tearing material open, also can hinder migration and the diffusion of lithium ion.Therefore, in order to improve LiFePO
4high rate performance, overcome carbon and be coated to LiFePO
4the negative effect that brings of energy density, the present invention is by introducing Graphene to LiFePO
4carry out composite modified.
Summary of the invention
The object of the present invention is to provide Graphene lithium iron phosphate battery anode composite material, solved existing anode material for lithium-ion batteries conductance low, surface coating layer complex process, expensive problem.
Another object of the present invention is also to provide a kind of preparation method of Graphene lithium iron phosphate battery anode composite material.
The technical solution adopted in the present invention is that Graphene lithium iron phosphate battery anode composite material is made up of Graphene and liFePO4 anode material for lithium-ion batteries; Wherein the mass percent scope of Graphene and liFePO4 anode material for lithium-ion batteries is 0.1%-8%.
Technical characterstic of the present invention is also that the component of liFePO4 anode material for lithium-ion batteries has lithium source, source of iron, phosphorus source and carbon source, wherein lithium source: source of iron: phosphorus source: carbon source is 1.0:0.95-1.0:0.95-1.0:0.1-0.5 according to mol ratio.Source of iron is one or more combination of iron powder, ferrous oxide, tri-iron tetroxide, di-iron trioxide, ferrous sulfate, ferric phosphate, ferrous oxalate; Phosphorus source is one or more combination of phosphorus pentoxide, phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ferrous ammonium phosphate ammonium hydrogen phosphate salt; Lithium source is one or more combination of lithia, lithium carbonate, lithium phosphate, lithium dihydrogen phosphate; Carbon source is one or more combination of carbon black, citric acid, glucose.
A preparation method for Graphene lithium iron phosphate battery anode composite material, is made up of following steps:
Step (1) is mixed presoma and is made, by lithium source: source of iron: phosphorus source: carbon source weighs according to mol ratio 1.0:0.95-1.0:0.95-1.0:0.1-0.5, adopts high temperature solid-state method to carry out pure phase LiFePO
4preparation, the material taking is put into ball mill mixing machine, using alcohol or pure water and zirconia ball or agate ball as ball-milling medium, according to material: ball: alcohol weight ratio 1:1.8-2:1.2-1.5 batch mixing fully mixes and within 4-16 hour, obtains presoma;
Step (2) preliminary treatment, is placed in 60-120 ℃ of drying oven by the presoma obtaining and dries alcohol or pure water, and naturally cooling rear grinding, obtains dusty material;
Step (3) sintering is synthetic, the powder obtaining in step (2) is put into tube furnace, after tube furnace being vacuumized with aspiration pump, pass into inert gas, in the stove of 600-850 ℃ in high temperature insulation reaction 2-10 hour, control is cooled to room temperature, obtains the coated liFePO4 anode material for lithium-ion batteries of carbon; Or the powder that step (2) preliminary treatment is obtained is put into tube furnace, in the tube furnace vacuumizing, pass into inert gas, under 0.1-20MPa high pressure, insulation reaction 1-12 hour in the stove of 300-700 ℃, control is cooled to room temperature, obtains the coated liFePO4 anode material for lithium-ion batteries of carbon;
The preparation of step (4) Graphene/liFePO4 battery anode composite material, adding Graphene in liFePO4 anode material for lithium-ion batteries coated carbon synthetic sintering in step (3), according to the weight ratio 0.1-8% of Graphene and the coated liFePO4 anode material for lithium-ion batteries of carbon, using alcohol or pure water and zirconia ball or agate ball as ball-milling medium, according to material: ball: the ratio of alcohol 1:1:1 is put into ball grinder mixing 8-12 hour, in the drying box of 60-120 ℃, dry alcohol or pure water, naturally cooling rear grinding, obtain Graphene/liFePO4 anode composite material of lithium ion battery.
This composite material takes full advantage of the good electric conductivity of Graphene, improved electronic conductivity, the discharge-rate performance of ferric phosphate lithium ion battery positive electrode, and Graphene fill process is simple, and price is low.
Accompanying drawing explanation
Fig. 1 is LiFePO of the present invention
4the positive electrode XRD figure that+4%graphite is compound;
Fig. 2 is LiFePO of the present invention
4matrix, LiFePO
4+ 1%graphite and LiFePO
4the XRD comparison diagram of+4%graphite;
Fig. 3 is pure phase LiFePO of the present invention
4the charge-discharge performance figure of matrix battery;
Fig. 4 is the 0.1C first charge-discharge song of pure phase LiFePO4 of the present invention and LiFePO4+4%graphite composite material.
Embodiment
Graphene lithium iron phosphate battery anode composite material of the present invention is made up of Graphene and liFePO4 anode material for lithium-ion batteries; Wherein the mass percent scope of Graphene and liFePO4 anode material for lithium-ion batteries is 0.1%-8%.The component of liFePO4 anode material for lithium-ion batteries has lithium source, source of iron, phosphorus source and carbon source, wherein lithium source: source of iron: phosphorus source: carbon source is 1.0:0.95-1.0:0.95-1.0:0.1-0.5 according to mol ratio.Source of iron is one or more combination of iron powder, ferrous oxide, tri-iron tetroxide, di-iron trioxide, ferrous sulfate, ferric phosphate, ferrous oxalate; Phosphorus source is one or more combination of phosphorus pentoxide, phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ferrous ammonium phosphate ammonium hydrogen phosphate salt; Lithium source is one or more combination of lithia, lithium carbonate, lithium phosphate, lithium dihydrogen phosphate; Carbon source is one or more combination of carbon black, citric acid, glucose.
The preparation method of Graphene lithium iron phosphate battery anode composite material of the present invention is as follows:
(1) mix presoma and make, by lithium source: source of iron: phosphorus source: carbon source, according to mol ratio 1.0:0.95-1.0:0.95-1.0:0.1-0.5, adopts high temperature solid-state method to carry out pure phase LiFePO
4preparation, the material taking is put into ball mill mixing machine, using alcohol (or pure water) and zirconia ball (or agate ball) as ball-milling medium, according to material: ball: alcohol weight ratio 1:1.8-2:1.2-1.5 batch mixing fully mixes and within 4-16 hour, obtains presoma.
(2) alcohol (or pure water) is dried the presoma obtaining in preliminary treatment in 60-120 ℃ of drying oven, and naturally cooling rear grinding, obtains dusty material.
(3) sintering is synthetic, the powder that preliminary treatment in step (2) is obtained is put into tube furnace, after tube furnace being vacuumized with aspiration pump, pass into inert gas, under inert gas or protective atmosphere, in the stove of 600-850 ℃ in high temperature insulation reaction 2-10 hour, and control and be cooled to room temperature under inert gas or protective atmosphere; Or the powder that (2) preliminary treatment is obtained, in inert gas or protective atmosphere, under additional 0.1-20MPa high pressure, in the stove of 300-700 ℃ under HTHP insulation reaction 1-12 hour, under inert gas or protective atmosphere, control and be cooled to room temperature.Obtain the coated liFePO4 anode material for lithium-ion batteries of carbon.
(4) Graphene/liFePO4 composite material preparation, adding Graphene in liFePO4 anode material for lithium-ion batteries coated carbon synthetic (3) sintering, according to the weight ratio 0.1-8% of Graphene and the coated liFePO4 anode material for lithium-ion batteries of carbon, using alcohol (or pure water) and zirconia ball (or agate ball) as ball-milling medium, according to material: ball: the ratio of alcohol 1:1:1 is put into ball grinder mixing 8-12 hour, at 60-120 ℃, in drying box, dry alcohol (or pure water), naturally cooling rear grinding, obtain Graphene/liFePO4 anode composite material of lithium ion battery.
(5), in technique scheme, the source of iron that the present invention adopts is one or more combination of iron powder, ferrous oxide, tri-iron tetroxide, di-iron trioxide, ferrous sulfate, ferric phosphate, ferrous oxalate.The phosphorus source that the present invention adopts is one or more combination of phosphorus pentoxide, phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ferrous ammonium phosphate ammonium hydrogen phosphate salt.The lithium source that the present invention adopts is one or more combination of lithia, lithium carbonate, lithium phosphate, lithium dihydrogen phosphate.The coated raw material of carbon that the present invention adopts is one or more combination of carbon black, citric acid, glucose.Meeting that the present invention introduces is Graphene or graphene oxide mutually.
Enumerating specific embodiment below describes:
Embodiment mono-: adopt lithium carbonate LiCO
3, ferrous oxalate FeC
2o
42H
2o, diammonium hydrogen phosphate (NH
4)
2hPO
4glucose C with the carbon source as coated
6h
12o
6for raw material, above-mentioned substance takes the quality of each material according to stoichiometry mol ratio 1.0:1.0:1.0:0.2, adopts high temperature solid-state method to carry out pure phase LiFePO
4preparation.The material taking is put into ball mill mixing machine, according to material: ball: alcohol 1:1.8:1.2 batch mixing 3h, puts into drying box and dries at 120 ℃ after discharging.After tube furnace being vacuumized with aspiration pump, pass into N
2, keep nitrogen pressure in 0.11MPa pressure left and right, the slow program to 700 ℃ of slow intensification is set, temperature retention time 8h.Keeping the synthetic coated pure phase LiFePO of carbon under high temperature, high pressure
4.In Fig. 2, can see synthetic pure phase LiFePO
4x-ray diffraction pattern.
Graphite(Graphene)/LiFePO
4the preparation of composite positive pole.Take synthetic pure phase LiFePO in a certain amount of step above
4, take Graphene according to the ratio of the weight ratio 4% of Graphene and the coated liFePO4 anode material for lithium-ion batteries of carbon, according to material: ball: the ratio of alcohol 1:1:1 is put into ball grinder and mixed 12 hours, after discharging, puts into 90 ℃ of oven dry of drying box.Obtain Graphene/LiFePO
4composite positive pole.In Fig. 1 and Fig. 2, can see synthetic Graphene/LiFePO
4the x-ray diffraction pattern of composite positive pole.
According to positive electrode: carbon black: the ratio of electrode adhesive Kynoar (PVDF)=0.8:0.1:0.1, take 1-METHYLPYRROLIDONE (NMP) as solvent, evenly be applied to and on aluminium foil, make positive plate, in the dry glove box of argon gas atmosphere, take metal lithium sheet as to electrode, Celgard2400 polypropylene screen is barrier film, ethylene carbonate (EC)+dimethyl carbonate (DMC)+1MLiPF
6for electrolyte, be assembled into button cell test performance.At the temperature of 25 ± 2 ℃, battery is carried out to constant current charge-discharge test in 2.5-4.2V voltage range.
Fig. 3 is LiFePO4 matrix battery first charge-discharge cycle performance figure at room temperature, the first discharge specific capacity of this sample under 0.1C charge-discharge magnification is 131.75mAh/g as can be seen from Figure, coulomb efficiency is 93.6%, after 10 charge and discharge cycles, specific discharge capacity is not almost decayed, for 117.47mAh/g, capability retention 90% left and right, discharge platform width ideal.
Fig. 4 is pure phase LiFePO
4and LiFePO
4+ 4%graphite composite material is with the multiplying power first charge-discharge curve of 0.1C.Gained LiFePO as seen from the figure
4the discharge voltage of/4%graphite composite positive pole is 3.4V.Under 0.1C charge-discharge magnification, pure phase LiFePO
4first discharge specific capacity reaches 131.75mAh/, pure phase LiFePO
4initial charge specific capacity reaches 140.76mAh/g; Under 0.1C charge-discharge magnification, LiFePO
4the first discharge specific capacity of+4%graphite composite material reaches 146.51mAh/, LiFePO
4the initial charge specific capacity of+4%graphite composite material reaches 157.7mAh/g.Can see, added the graphite of the constant weight percentage material after compound, charging performance has improved 12%; Discharge performance has improved 11.2%.Its charge-discharge performance is significantly improved.
Compared with the preparation method of this method and other traditional lithium ion battery anode material lithium iron phosphate, process costs does not significantly increase, and can realize effective introducing of the coated and Graphene of good carbon, reaches the object of improving performance.The present invention adopts glucose, as carbon source, material is carried out to carbon and is coated, and reaches the object of starvation and reduction.Because the increase of conductive carbon material addition can cause LiFePO
4the tap density of/C material sharply declines, and therefore partial thermal decomposition carbon is replaced to Graphene by the present invention, and the composite conducting network that has a Graphene and RESEARCH OF PYROCARBON to form improves the chemical property of active material.Resulting materials charging and discharging capacity is respectively 121.3mAh/g and 112.7mAh/g, and coulomb efficiency is 90% left and right, discharge platform width ideal, and after multiple charge and discharge cycles, specific discharge capacity is not almost decayed, and has improved LiFePO
4the problem that conductivity is low and lithium ion diffusion rate is slow, is suitable for making power battery anode material.
The Graphene that the present invention adopts is a kind of coated structure of modification that is well suited for carrying out.Add a small amount of Graphene not change LiFePO
4olivine-type structure and Pnmb space group, just structure is played to a slight modification, small change cell parameter and and unit cell volume change, also played the effect that increases chemical property simultaneously, and do not change physical structure, in the material that has proved to fill a prescription, there is no unreacted impurity, LiFePO simultaneously yet
4structural integrity, there is specific chemical property itself.
The present invention be advantageous in that:
(1) under the condition of inert gas or protective atmosphere, adopt the way of high temperature or HTHP combination, synthesize the liFePO of pure phase
4crystalline phase, has avoided ferrous iron to be easy to be oxidized to the shortcoming that ferric iron causes performance of lithium ion battery to decline, and has also reduced reaction-sintered temperature, sintering time simultaneously.
(2) good carbon can be realized in raw material mix stages introducing carbon source coated, the tap density of positive electrode, utilance and the discharge cycles performance of active material can be improved.In composite material, introduce Graphene as electric conductivity modifier, can significantly improve the charge-discharge performance of lithium ion battery.
(3) under the condition of inert gas or protective atmosphere, adopt the way of high temperature or HTHP combination, the advantages of good crystallization of material, crystal particle scale is less, is difficult for reuniting, and actual capacity is high, and reversibility is good.Raw material sources are extensive, the battery of Graphene/liFePO4 composite material that the present invention is synthetic and metal lithium sheet assembling, test as example take 0.1 rate charge-discharge, when charging voltage is 2.5-4.2V, charge/discharge capacity has improved 12% left and right than liFePO4 material, after circulating 10 weeks, capability retention still reaches more than 90%.
Claims (4)
1. a Graphene lithium iron phosphate battery anode composite material, is characterized in that: be made up of Graphene and liFePO4 anode material for lithium-ion batteries; Wherein the mass percent scope of Graphene and liFePO4 anode material for lithium-ion batteries is 0.1%-8%.
2. according to a kind of Graphene lithium iron phosphate battery anode composite material described in claim 1, it is characterized in that: the component of described liFePO4 anode material for lithium-ion batteries has lithium source, source of iron, phosphorus source and carbon source, wherein lithium source: source of iron: phosphorus source: carbon source is 1.0:0.95-1.0:0.95-1.0:0.1-0.5 according to mol ratio.
3. according to a kind of Graphene lithium iron phosphate battery anode composite material described in claim 1, it is characterized in that: described source of iron is one or more combination of iron powder, ferrous oxide, tri-iron tetroxide, di-iron trioxide, ferrous sulfate, ferric phosphate, ferrous oxalate; Described phosphorus source is one or more combination of phosphorus pentoxide, phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ferrous ammonium phosphate ammonium hydrogen phosphate salt; Described lithium source is one or more combination of lithia, lithium carbonate, lithium phosphate, lithium dihydrogen phosphate; Described carbon source is one or more combination of carbon black, citric acid, glucose.
4. according to the preparation method of Graphene lithium iron phosphate battery anode composite material described in claim 1, it is characterized in that carrying out according to following steps:
Step (1) is mixed presoma and is made, by lithium source: source of iron: phosphorus source: carbon source weighs according to mol ratio 1.0:0.95-1.0:0.95-1.0:0.1-0.5, adopts high temperature solid-state method to carry out pure phase LiFePO
4preparation, the material taking is put into ball mill mixing machine, using alcohol or pure water and zirconia ball or agate ball as ball-milling medium, according to material: ball: alcohol weight ratio 1:1.8-2:1.2-1.5 batch mixing fully mixes and within 4-16 hour, obtains presoma;
Step (2) preliminary treatment, is placed in 60-120 ℃ of drying oven by the presoma obtaining and dries alcohol or pure water, and naturally cooling rear grinding, obtains dusty material;
Step (3) sintering is synthetic, the powder obtaining in step (2) is put into tube furnace, after tube furnace being vacuumized with aspiration pump, pass into inert gas, in the stove of 600-850 ℃ in high temperature insulation reaction 2-10 hour, control and be cooled to room temperature and obtain the coated liFePO4 anode material for lithium-ion batteries of carbon; Or the powder that step (2) preliminary treatment is obtained is put into tube furnace, passes into inert gas in the tube furnace vacuumizing, under 0.1-20MPa high pressure, insulation reaction 1-12 hour in the stove of 300-700 ℃, controls and is cooled to room temperature; Obtain the coated liFePO4 anode material for lithium-ion batteries of carbon;
The preparation of step (4) Graphene/liFePO4 battery anode composite material, adding Graphene in liFePO4 anode material for lithium-ion batteries coated carbon synthetic sintering in step (3), according to the weight ratio 0.1-8% of Graphene and the coated liFePO4 anode material for lithium-ion batteries of carbon, using alcohol or pure water and zirconia ball or agate ball as ball-milling medium, according to material: ball: the ratio of alcohol 1:1:1 is put into ball grinder mixing 8-12 hour, in the drying box of 60-120 ℃, dry alcohol or pure water, naturally cooling rear grinding, obtain Graphene/liFePO4 anode composite material of lithium ion battery.
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| CN108695511A (en) * | 2017-04-07 | 2018-10-23 | 王宏栋 | Lithium ion battery material surface coated with conductive layer and preparation method thereof |
| CN108695511B (en) * | 2017-04-07 | 2021-04-02 | 王宏栋 | Lithium ion battery material surface coating conductive layer and preparation method thereof |
| CN107275606B (en) * | 2017-06-13 | 2020-03-17 | 山东大学 | Carbon-coated spinel lithium manganate nanocomposite and preparation method and application thereof |
| CN107275606A (en) * | 2017-06-13 | 2017-10-20 | 山东大学 | A kind of carbon coating spinel lithium manganate nano composite material and preparation method and application |
| CN109103433A (en) * | 2018-08-22 | 2018-12-28 | 江苏元景锂粉工业有限公司 | A kind of nitrogen mixes carbon-coated lithium iron phosphate composite and preparation method thereof |
| CN110828780A (en) * | 2019-11-01 | 2020-02-21 | 长沙矿冶研究院有限责任公司 | graphene/TiO2Preparation method of composite positive electrode |
| CN114057188A (en) * | 2020-11-06 | 2022-02-18 | 江苏清联光电技术研究院有限公司 | Graphene preparation method |
| CN113651304A (en) * | 2021-08-09 | 2021-11-16 | 天津理工大学 | Organic carbon-coated lithium iron phosphate cathode material and preparation method thereof |
| CN113651304B (en) * | 2021-08-09 | 2023-10-13 | 天津理工大学 | Organic carbon coated lithium iron phosphate positive electrode material and preparation method thereof |
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