CN110429249A - A kind of preparation method of rubber removing graphene combination electrode material - Google Patents
A kind of preparation method of rubber removing graphene combination electrode material Download PDFInfo
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- CN110429249A CN110429249A CN201910640273.5A CN201910640273A CN110429249A CN 110429249 A CN110429249 A CN 110429249A CN 201910640273 A CN201910640273 A CN 201910640273A CN 110429249 A CN110429249 A CN 110429249A
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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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Abstract
The present invention is the preparation method that a kind of rubber removes graphene combination electrode material.This method utilizes mechanical power drive rubber Boli scale graphite, expansible graphite or expanded graphite, separate its piece interlayer gradually, after forming single layer or few layer graphene or graphene oxide compounded rubber block, the energy storage active substances such as LiFePO4 are added among compounded rubber again, be kneaded, fall glue and packing, formed graphene or graphene energy storage active substance it is evenly dispersed-the compound blob of viscose of energy storage active substance-rubber；Through high-temperature roasting, energy storage active substance-graphene mix-froth gel is obtained, the positive electrode and negative electrode material of lithium ion battery are finally prepared into.The present invention can increase substantially traditional lithium-ion battery high magnification charging-discharging performances, improve charging rate.
Description
Technical field
The present invention relates to a kind of using mechanical power drive rubber molecule Boli scale graphite, and the graphene of formation is raw material,
The method for preparing high performance electrode material belongs to the preparation of graphene and the application in energy storage field.
Background technique
It by lithium metal or lithium alloy is negative electrode material, using the battery of non-aqueous electrolytic solution that lithium ion battery, which is a kind of,
The advantages that specific energy with higher, lower self discharge, long circulation life, battery structure be stable, memory-less effect, as shifting
Dynamic power supply, finds broad application in various fields such as communication, computer, communications and transportation, aerospaces.It ties in the duct of electrode material
The optimization of structure and surface characteristics, thus it is possible to vary the performance of lithium ion battery, studies have shown that passing through the specific surface for improving electrode material
Product, cellular structure and electric conductivity, which can achieve, improves its chemical property.And the composition of lithium ion cell electrode positive electrode and
Structure is affected to battery capacity, cycle-index, charge-discharge magnification etc., and common positive electrode has LiMO2(M=Ni, Co
Deng), LiFePO4 (LPF), ternary material (LiNixCoyMnO2) etc..Although the LiCoO of layer structure2It is that earliest commercialization is answered
Positive electrode, but since cobalt resource is rare, expensive, the disadvantages of thermal stability is poor, use is not extensive.Ternary material
The advantages of combining multiple material, but manufacturing condition is harsh, higher cost, safety are poor, and technology of preparing is still to further
It breaks through.And with olivine-type structure LiFePO4 specific capacity it is high, it is nontoxic, cheap, have a safety feature, become in recent years
One of most popular power battery anode material, but the conductivity of LiFePO4 is low, lithium ion mobility is lower, for that purpose it is necessary to plus
Enter the conductive agents active material such as conductive black, carbon nanotubes, graphene, improves the electric conductivity of anode.
Studies have shown that the electric conductivity that graphene is excellent, makes it have good application in anode material for lithium-ion batteries
Prospect.Such as graphene and LiFePO 4 material are mixed, the conductivity of LiFePO4 theoretically can be improved, promotes times of battery
Rate performance.Its reason is: graphene can significantly improve the dispersibility of LiFePO4 particle, form three-dimensional conductive network, change
Kind material conductivity improves high rate performance to improve material capacity to greatest extent.Related graphene is as lithium ion battery material
The patent of material not only includes cathode (cathode) material, also there is a large amount of anode (anode) material.
Lithium ion battery be using 2 kinds of different lithium intercalation compounds that can be reversibly inserted into and deviate from lithium ion as
The anode of battery and 2 primary cell systems of cathode.The anode of lithium ion battery, the composition material of cathode include: electrode activity thing
Matter carbon material or non-carbon material, adhesive and additive are mixed and made into paste adhesive, are uniformly applied to aluminium foil, copper foil two respectively
Side, through drying, rolling into anode, negative electrode material, performance depend on can preparing reversibly de-/embedding lithium ion just,
Negative electrode material.Patent such as CN109585849A, CN109546083A, CN106159245A as cathode material,
CN107507967A, CN107394185A, CN108807932A etc.；Positive electrode accounting in lithium ion battery is larger, property
The performance of lithium ion battery can be directly affected, cost also directly affects battery price.Related graphene lithium battery anode material
In terms of the preparation patent of material, ZL 201310459260, CN105206799A, CN106711447A, CN107331845A,
CN108807992A、
CN109037560A、CN109037666A、CN109119616A、CN108493397A、CN109290155A、
CN108878842A,CN108807897A；These cathode or positive electrode are using commercially available graphene, or in strong acid environment
In aoxidize crystalline flake graphite, formed graphene oxide, utilize after carrying out reduction, or the doping metals in electrically conductive graphite, improve electrode
The specific capacity and electric conductivity of material.Commercially available graphene used in the above method, not only preparation cost is high, wastewater discharge
Greatly, environmental problem is not only brought, and the black huge specific surface area of alkene makes it have high surface energy and surface-active, is making
In standby, dispersion, dry, storage and transport process, easily reunites and " be graphitized " again；Using conventional stirring mixing method, it is difficult to make
Its base that the energy storage active substances such as LiFePO4, cobalt acid lithium, LiMn2O4 are evenly spread to the state of single layer or few layer graphene
In body, three-dimensional conductive network structure is formed.
Summary of the invention
It is an object of the present invention to provide a kind of rubber removing graphene combination electrode material for deficiency existing for current techniques
The preparation method of material.This method utilizes mechanical power drive rubber Boli scale graphite (correspondence separates graphene) or inflatable
Graphite, expanded graphite (correspondence separates graphene oxide), separate its piece interlayer gradually, formation single layer or less layer graphene,
Or after graphene oxide compounded rubber block, then the energy storage active substances such as LiFePO4 are added to graphene or graphene oxide
Compounded rubber among, be kneaded, fall glue and packing, form the evenly dispersed graphene-energy storage of graphene, energy storage active substance
The compound blob of viscose of active material-rubber or graphene oxide-compound blob of viscose of energy storage active substance-rubber；Through high-temperature roasting, make to have
The decomposition of machine object, charing, the reduction of graphene oxide, acquisition energy storage active substance-graphene composite foam gel, and in this, as
The raw material of electrical conductive activities substance, ground, addition adhesive and solvent mix, and coated, dry, press mold is prepared into lithium ion
The positive electrode and negative electrode material of battery, to increase substantially traditional lithium-ion battery high magnification charging-discharging performances, raising is filled
Electric speed.
The technical solution of the present invention is as follows:
A kind of preparation method of rubber removing graphene combination electrode material, method includes the following steps:
Step 1: the removing of graphite flake layer
Rubber matrix and graphite raw material are added in mixer, after mixing 3-20min, double rod open mills is transferred to and is mixed
10-60min is refined, the compounded rubber block containing graphene or graphene oxide 4~45% is obtained；
Wherein, the mass ratio of rubber matrix and graphite raw material is 100:5-70；
Step 2: energy storage active substance is mixed into
Upper step is obtained into the twin rollers that compounded rubber block is added in operating, after rolling packet roller, energy storage active matter is added
Powder and dioctyl phthalate 5-30ml are kneaded 10-30 minutes, form graphene-energy storage active substance-rubber compound adhesive
Piece or graphene oxide-compound film of energy storage active substance-rubber；
Wherein, the quality of energy storage active matter is the 3-9 of institute's containing graphene or graphene oxide quality in compounded rubber block
Times；
Step 3: the charing of compounded rubber
Graphene or graphene oxide-energy storage active substance-compounded rubber piece that upper step obtains are put into crucible, added
Lid, is placed into heating equipment, and 10~50min of heat preservation roasting, obtains energy storage active substance-graphene carbon at 500~1000 DEG C
Change foams；
Step 4: energy storage active substance-graphene carbonized foams body grinding distribution
- 350 mesh of 200 mesh will be crossed after energy storage active substance-graphene carbonized foams body grinding, obtains energy storage active matter
Matter-graphene conductive agent active powder；
Energy storage active substance-graphene carbonized foams body in the step 4 is ground to hand lapping in mortar, or
Ball mill grinding in ball grinder, drum's speed of rotation are 400~1000rpm, grind 15~60min, pellet mass ratio 1:2-4, mill
Ball is the zirconium oxide of diameter 2mm.
The application of the rubber removing graphene combination electrode material, the group for graphene fastening lithium ionic cell
Dress.
The following steps are included:
(1) preparation of graphene lithium ion battery anode pole piece
It is added adhesive into energy storage active substance-graphene conductive agent active powder, after magnetic agitation 3h-10h, drop
After entering solvent, continue to stir 3h-6h formation grume mixture；By grume mixture even application on aluminium foil, it is put into true
Empty drying box is dry, and film forming is suppressed on double rod film laminators, and cuts and the pole piece of diameter 14mm is made obtains working electrode；
Wherein, adhesive quality is energy storage active matter-graphene conductive agent active powder 5%-10%；Solvent is added
Volume (ml) and energy storage active substance-graphene conductive agent active powder quality (g) ratio be 1-4:1；Aluminium foil list
The coated weight of plane product is the amount 5mg/cm of grume mixture2-20mg/cm2, after drying after to roller membrane pressure, formed with a thickness of
50 μm of -120 μm of homogeneous conductive films；
(2) it in the vacuum glove box full of argon gas, is positive pole with corresponding positive electrode diaphragm obtained, metal lithium sheet is
Cathode, 1M LiPF6/ dimethyl carbonate (DMC)+ethylene carbonate (EC)+methyl ethyl carbonate (EMC) (volume ratio 1:1:1) are
Electrolyte, Celgard2400 microporous polypropylene membrane is the assembling that diaphragm carries out different model button cell, by assembled battery
It is put into copper mold and is tightened with pliers, obtain the lithium ion battery that roasting rubber removing graphene is positive conductive material；
Charge-discharge performance test recycles battery under room temperature (25 ± 1 DEG C), is forthright again using Land test macro
It can test, test voltage is between 3.5V-4.95V.
Graphite raw material described in step 1 is crystalline flake graphite, expanded graphite and expansible graphite；
The rubber matrix includes: natural rubber, butadiene-styrene rubber, ethylene propylene diene rubber, neoprene or nitrile rubber；
Energy storage active matter described in step 2 refers to LiFePO4, cobalt acid lithium or LiMn2O4.
Heating equipment described in step 3 includes: the carbonizations such as micro-wave oven, tube furnace, Muffle furnace or vacuum sintering furnace roasting；
Roasting is carried out under the nitrogen of certain flow or atmosphere of hydrogen described in step 3；When graphite raw material is crystalline flake graphite,
Atmosphere is nitrogen；When graphite raw material is expanded graphite or expansible graphite, atmosphere is hydrogen；Gas flow is 0.005L/
Min-5L/min, the pressure of vacuum drying oven are 0.1pa-100pa；
Step 5 described adhesive refers in Kynoar, polyacrylic acid, polyvinyl alcohol, gelatin, carboxymethyl cellulose etc.
One kind；
Solvent described in step 5 is n,N-Dimethylformamide, O-phthalic alkanol amides, N-Methyl pyrrolidone and two
The mixture of one or both of methylacetamide；
Substantive distinguishing features of the invention are as follows:
This patent proposes to be formed using mechanical power drive rubber Boli scale graphite, expansible graphite or expanded graphite etc.
Graphene or the higher uniform graphene of graphene oxide content, graphene oxide compounded rubber block；Then be added LiFePO4,
The energy storage active substances such as cobalt acid lithium, LiMn2O4 continue with the mechanical force of twin rollers, are evenly spread to graphene, oxidation
In the compound rubber blocks of graphene, through high-temperature roasting, decompose rubber matrix, carbonization, and make the oxidation stone in rubber matrix
Black alkene is reduced into graphene in reducing atmosphere or the CO gas formed, to form energy storage active substance-graphite
Alkene composite foam block particle, ground, sieving obtain uniform energy storage active substance-graphene energy storage conductive agent active matter；
It is mixed again with adhesive, solvent, forms paste, through gluing, dry, press mold is cut out and assembled, high magnification is made and fills, put
The lithium ion battery of excellent electrical property.This is a kind of efficient, cheap, batch acquisition high-performance energy storage active substance-graphene
The method of conductive material raw material can be mentioned significantly as the positive electrode of lithium ion battery, negative electrode material or capacitor material
The high magnification charging-discharging performances of high traditional lithium-ion battery improve charging rate and capacity and energy density.
The invention has the benefit that
Using mechanical power drive rubber Boli scale graphite, expansible graphite or expanded graphite, make between graphite flake layer gradually
Separation, the content for forming graphene are up to 40% single layer or few layer graphene, graphene oxide compounded rubber block；Then it is added
The energy storage active substances such as LiFePO4, cobalt acid lithium, LiMn2O4 continue with mechanical force and are evenly spread to graphene, oxidation
It in graphene compounded rubber block, is roasted through micro-wave oven, tube furnace, vacuum drying oven, makes there is rubber matrix to decompose, carbonize, aoxidize stone
Black alkene is reduced into graphene, forms energy storage active substance-graphene uniform mixing, and mutually interspersed has three-dimensional conductive network knot
The composite foam block particle of structure, ground, sieving obtain uniform energy storage active substance-graphene energy storage conductive agent activity
Object；And as energy storage, conductive material raw material, it is prepared into the positive electrode or negative electrode material of lithium ion battery.To as implemented
For 1 charging and discharging curve of example compared with the lithium ion battery of commercially available graphene anode material, the 5C charge and discharge of commercially available graphene battery are bent
Quickly, 5C charging performance is only the 65.1% of 1 sample of embodiment to line attenuation, and discharge performance is 66.9%；It can be seen that utilizing this
The rubber of invention removes graphene, and being combined mechanical force can be fully dispersed to graphene compounded rubber by energy storage active substance
Matrix in, then by Roasting Decomposition, form uniform energy storage active substance-graphene mixed powder, be conducive to contract after film
The distance of short ion transmission, to increase substantially the high magnification charging-discharging performances of lithium ion battery.
Detailed description of the invention
Fig. 1 is the neoprene mixing crystalline flake graphite in embodiment 1, commercially available graphene and neoprene Boli scale graphite
The X-ray diffracting spectrum of formation.
Fig. 2 is that the positive electrode as lithium ion battery of 1 sample of embodiment is assembled into the charging and discharging curve of button cell；
Fig. 3 is that the commercially available graphene of ratio same as Example 1 is added in LiFePO4, just as lithium ion battery
Pole material is assembled into the charge and discharge curve of button cell；It can be seen that its big multiplying power charge and discharge curve, especially 5C charge and discharge curve
Quickly, 5C charging curve is the 65.1% of 1 sample of embodiment, and discharge performance is 66.9% for decaying；
Fig. 4 is the charging and discharging curve that 2 sample of embodiment is assembled into button cell as the positive electrode of lithium ion battery；
Specific embodiment
Material of the present invention is specially the graphene for using different type rubber to remove, the compounded rubber of graphene oxide
The graphene carbonized foams formed after block, and its roasting, the graphene formed after grinding；The commercially available stone that control sample uses
Black alkene is graphene new material Co., Ltd, Qitaihe treasured ACE Semi product.
The experiment height that crystalline flake graphite is that commercially available crystalline flake graphite miberal powder manufacturer is Lingshou County Shuo Long mineral products processing factory
Pure crystalline flake graphite；Expansible graphite is purchased from Qingdao Chen Yang graphite Co., Ltd；Expanded graphite is to have using Qingdao morning sun graphite
The expansible graphite of limit company is put into 1000 DEG C of Muffle furnaces, is kept the temperature 100s, was taken out the oversize of 40 mesh standard sieves.
LiFePO4 is the technical grade powder of Tianjin Si Telan energy science and technology limited liability company production, is pure phase ferric phosphate
Lithium, after ultrasonic disperse, partial size D97=2.15 μm.
Embodiment 1
The removing of step 1 graphite flake layer
Neoprene 100g is added in the mixer of 0.2L, and crystalline flake graphite crystal 30g is added, is switched on, mixing 15min
Afterwards, it takes out, is transferred to two-roll mill and continues to be kneaded 30min, the neoprene that the mass percent for obtaining graphene is 23% is shelled
From the compound blob of viscose of graphene.(revolving speed of mixer is 40rpm；To the two wheel guide robot 1:1.3 of roller open mill, front wheel rotation speed is
18.6rpm)
Step 2 LiFePO4 machinery is mixed into
The graphene content for weighing step 1 preparation is that 23% neoprene removes the compound blob of viscose 100g of graphene, is put into fortune
In twin rollers roller in turning, roll-in packet roller (in 1min), is gradually added LiFePO 4 powder 140g and phthalic acid two is pungent
Ester 30ml mixes roll-in 30min, and during which the LiFePO 4 powder trickled down outside roller is all returned to being mixed into colloid on roller
In, then beat triangle bag 10 times, thin pass-out piece, form uniform graphene-compound blob of viscose of LiFePO4-rubber；
The charing of the compound blob of viscose of step 3
Step 2 is prepared neoprene removing graphene-compound blob of viscose of LiFePO4-rubber to be put into porcelain boat, is put into
It in 800W micro-wave oven, is passed through nitrogen and heats 20min, control nitrogen flow 1L/min, the graphene-phosphoric acid for preparing step 2
Iron lithium-compound blob of viscose of rubber sufficiently carbonizes, and forms LiFePO4-graphene carbonized foams body；
Step 4 LiFePO4-graphene carbonized foams body grinding distribution
LiFePO4-graphene carbonized foams body prepared by step 3 is put into ball grinder, is 1:4 by pellet mass ratio
Diameter 2mm zirconium oxide abrasive ball is added, in drum's speed of rotation 1000rpm, grinds 15min, crosses 325 meshes, lower part of screen is divided into
LiFePO4-graphene conductive agent active powder, i.e. combination electrode material；
The preparation of step 5 graphene lithium ion battery anode pole piece
Powder quality 7.5% is added in the LiFePO4 made from step 4-graphene conductive agent active powder and gathers inclined fluorine
Polyethylene adhesive after magnetic agitation 6h, is added the isometric N-Methyl pyrrolidone solvent of powder quality, continues to stir 5h, shape
At uniform sticky mixture, sticky mixture material is pressed into 20mg/cm2On the uniform aluminium foil coated in 16 μ m-thicks, it is put into true
120 DEG C of empty drying box dry 12h, are pressed into uniform film on double rod film laminators, and cut and the pole piece of diameter 14mm is made makes
Working electrode is obtained, puts the electrodes into the vacuum glove box full of argon gas and recycles 4h, it is spare；
The assembling of step 6 graphene fastening lithium ionic cell
It in the vacuum glove box full of argon gas, is positive pole with corresponding positive electrode diaphragm obtained, metal lithium sheet is negative
Pole, 1MLiPF6/ dimethyl carbonate (DMC)+ethylene carbonate (EC)+methyl ethyl carbonate (EMC) (volume ratio 1:1:1) are electricity
Liquid is solved, Celgard2400 microporous polypropylene membrane is the assembling that diaphragm carries out CR2032 type button cell, and assembled battery is put
Enter in copper mold and tightened with pliers, obtains the lithium ion battery that rubber removing graphene is positive conductive material；
The charge-discharge performance of embodiment sample is tested, using Land test macro under room temperature (25 ± 1 DEG C) to battery into
Row circulation, high rate performance test, for test voltage between 3.5V-4.95V, embodiment 2- embodiment 6 is identical.
The charge-discharge test curve of the lithium ion battery is shown in Fig. 2, with the electrical conductive activities object of commercially available graphene and same ratio
The charging and discharging curve that the control sample of preparation is mixed in matter is shown in Fig. 3, and the test result of different multiplying charge-discharge performance sees attached list 1
The scale before the graphene Composite Milk blob of viscose formed to neoprene Boli scale graphite in embodiment and removing
The mixing blob of viscose of graphite mixing neoprene, three samples of commercially available graphene carry out X-ray diffraction analysis, and obtained result is shown in
Fig. 1, from the comparison of the diffracting spectrum of sample as can be seen that mixing blob of viscose (above a curve) In of crystalline flake graphite neoprene
The diffraction peak intensity that 2 angles θ are 26.56 ° is 147466, and removing forms the diffraction of the compound blob of viscose of graphene (a following curve)
Peak intensity is only 1151, diffraction peak intensity only rubber mix crystalline flake graphite diffracted intensity 0.78%, and peak half-breadth substantially increases
Add, shows that crystalline flake graphite is removed to form graphene blob of viscose by rubber；
The diffraction peak intensity (an intermediate curve) of commercially available graphene forms graphite much higher than removing for 17190 in Fig. 1
The 1151 of the compound blob of viscose of alkene, declaratives graphene had occurred in storage and transport process it is a degree of reunite again, have it is secondary
" graphitization " trend, it is difficult to be uniformly distributed among LiFePO4 by simple mechanical stirring, form three-dimensional conductive net
Therefore network structure, electron mobility are obstructed and decline charging-discharging performances, be to influence its big multiplying power as cell positive material
Charging-discharging performances, the especially key of 5C charge-discharge performance.
It is roasting after neoprene removing graphene is electrical conductive activities raw material of substance, with LiFePO4 mechanical mixture from Fig. 2
LiFePO4-graphene carbonized foams are formed, ground, addition adhesive, coating, is dried, after press mold at solvent modulation, as
The anode of lithium ion battery is assembled into the charging and discharging curve of button cell, and compared to its low range charging-discharging performances, 5C is filled, put
Though electrical property decreases, overall to keep higher level；
Fig. 3 is that the commercially available graphene of ratio same as Example 1 is added in LiFePO4, is fully ground, and is added viscous
After mixture, solvent modulation, coating, drying, press mold, the charge and discharge that the anode as lithium ion battery is assembled into button cell are bent
Line；It can be seen that the decaying of its big multiplying power charge and discharge curve, especially 5C charge and discharge curve is quickly, 5C charging curve is 1 sample of embodiment
The 65.1% of product, and discharge performance is 66.9%；
Embodiment 2
The removing of step 1 graphite flake layer
Nitrile rubber 100g is added in the mixer of 0.2L, and crystalline flake graphite crystal 40g is added, is switched on, mixing 15min
Afterwards, it takes out, is transferred to two-roll mill and continues to be kneaded 50min, obtain the butyronitrile rubber that graphene mass percentage content is 28.6%
Glue removes the compound blob of viscose of graphene.
Step 2 LiFePO4 machinery is mixed into
The graphene content for weighing step 1 preparation is that 28.6% nitrile rubber removes the compound blob of viscose 100g of graphene, is put into
In twin rollers roller in operating, it is kneaded packet roller, is gradually added LiFePO 4 powder 114g and dioctyl phthalate 15ml,
Roll-in 15min is mixed, during which the LiFePO 4 powder trickled down outside roller is all returned to and is mixed into colloid on roller, then makes a call to three
Angle is wrapped 10 times, and thin pass-out piece forms uniform graphene-compound blob of viscose of LiFePO4-rubber；
The charing of the compound blob of viscose of step 3
Step 2 is prepared nitrile rubber removing graphene-compound blob of viscose of LiFePO4-rubber to be put into porcelain boat, loading tube
It in formula furnace, is passed through nitrogen and heats, control nitrogen flow 2L/min, 20 DEG C/min of heating rate is warming up to 700 DEG C, at 700 DEG C
20min is kept the temperature, the nitrile rubber removing graphene-compound blob of viscose of LiFePO4-rubber for preparing step 2 sufficiently carbonizes, and is formed
LiFePO4-graphene carbonized foams body；
Step 4 LiFePO4-graphene carbonized foams body grinding distribution
LiFePO4-graphene carbonized foams body prepared by step 3 is put into ball grinder, is 1:2 by pellet mass ratio
Diameter 2mm zirconium oxide abrasive ball is added, in drum's speed of rotation 700rpm, grinds 50min, crosses 300 meshes, lower part of screen is divided into phosphorus
Sour iron lithium-graphene conductive agent active powder, i.e. combination electrode material；
The preparation of step 5 graphene lithium ion battery anode pole piece
10% gelatin of powder quality, magnetic are added in the LiFePO4 made from step 4-graphene conductive agent active powder
Power stirs 8h, and powder quality 7.5%N- methyl pyrrolidone solvent is added, and continues to stir 6h, forms uniformly sticky mixture, will
Sticky mixture material presses 10mg/cm2On the uniform aluminium foil coated in 16 μ m-thicks, it is put into 120 DEG C of dryings of vacuum oven
12h suppresses film forming on double rod film laminators, and cuts and the pole piece of diameter 14mm is made obtains working electrode, puts the electrodes into and fills
4h is recycled in the vacuum glove box of full argon gas, it is spare；
The assembling of step 6 graphene fastening lithium ionic cell
It in the vacuum glove box full of argon gas, is positive pole with corresponding positive electrode diaphragm obtained, metal lithium sheet is negative
Pole, 1MLiPF6/ dimethyl carbonate (DMC)+ethylene carbonate (EC)+methyl ethyl carbonate (EMC) (volume ratio 1:1:1) are electricity
Liquid is solved, Celgard2400 microporous polypropylene membrane is the assembling that diaphragm carries out CR2032 type button cell, and assembled battery is put
Enter in copper mold and tightened with pliers, obtains the lithium ion battery that rubber removing graphene is positive conductive material；
The charge and discharge test curve of the embodiment lithium ion battery is shown in Fig. 4, different multiplying charging-discharging performances test result
See attached list 1
Embodiment 3
The removing of step 1 graphite flake layer
Natural rubber 100g is added in the mixer of 0.2L, and expansible graphite crystal 20g is added, is switched on, mixing
It after 10min, takes out, is transferred to two-roll mill and continues to be kneaded 50min, obtaining graphene oxide mass percentage content is 16.8%
Natural rubber remove the compound blob of viscose of graphene oxide.
Step 2 LiMn2O4 machinery is mixed into
The graphene oxide content for weighing step 1 preparation is that 16.8% natural rubber removes the compound blob of viscose of expansible graphite
100g is put into the twin rollers roller in operating, and roll-in packet roller, is gradually added mangaic acid powder for lithium 84g and phthalic acid two is pungent
Ester 5ml mixes roll-in 10min, is during which all returned to the LiFePO 4 powder trickled down outside roller and is mixed into colloid on roller,
It beats again triangle bag 10 times, thin pass-out piece, forms graphene oxide-compound blob of viscose of LiMn2O4-rubber；
The charing of the compound blob of viscose of step 3
Step 2 is prepared natural rubber removing graphene oxide-compound blob of viscose of LiMn2O4-rubber to be put into porcelain boat, is put into
Vacuum sintering furnace, combined floodgate vacuumize, and heat, and furnace pressure controls the heating rate 20 DEG C/min liter between 0.05pa-10pa
Temperature keeps the temperature 50min to 600 DEG C, and the compound blob of viscose of the graphene oxide-LiMn2O4-rubber for preparing step 2 is decomposed, sufficiently carbonized,
Graphene oxide is reduced, and forms LiMn2O4-graphene carbonized foams body；
Step 4 LiMn2O4-graphene carbonized foams body grinding distribution
LiMn2O4-graphene carbonized foams body prepared by step 3 is put into ball grinder, is added by pellet mass ratio for 1:2
Enter diameter 2mm zirconium oxide abrasive ball, in drum's speed of rotation 800rpm, grinds 45min, cross 250 meshes, lower part of screen is divided into mangaic acid
Lithium-graphene conductive agent active powder, i.e. combination electrode material；
The preparation of step 5 graphene lithium ion battery anode pole piece
5% carboxymethyl cellulose of powder quality is added in the LiMn2O4 made from step 4-graphene conductive agent active powder
Element after magnetic agitation 10h, after instilling the O-phthalic alkanol amides solvent of powder quality 5%, continues to stir 3h, be formed equal
Sticky mixture material is pressed 5mg/cm by even grume mixture2It is uniform to be coated on the aluminium foil of 16 μ m-thicks, it is put into vacuum
120 DEG C of drying box dry 12h, on double rod film laminators suppress film forming, and cut be made diameter 14mm pole piece obtain work electricity
Pole puts the electrodes into the vacuum glove box full of argon gas and recycles 4h, spare；
The assembling of step 6 graphene fastening lithium ionic cell
It in the vacuum glove box full of argon gas, is positive pole with corresponding positive electrode diaphragm obtained, metal lithium sheet is negative
Pole, 1MLiPF6/ dimethyl carbonate (DMC)+ethylene carbonate (EC)+methyl ethyl carbonate (EMC) (volume ratio 1:1:1) are electricity
Liquid is solved, Celgard2400 microporous polypropylene membrane is the assembling that diaphragm carries out CR2032 type button cell, and assembled battery is put
Enter in copper mold and tightened with pliers, obtains the lithium ion battery that rubber removing graphene is positive conductive material；
The charging-discharging performances test result of the battery different multiplying sees attached list 1
Embodiment 4
The removing of step 1 graphite flake layer
Ethylene propylene diene rubber 100g is added in the mixer of 0.2L, and crystalline flake graphite crystal 70g is added, is switched on, mixing
It after 20min, takes out, is transferred to two-roll mill and continues to be kneaded 60min, obtain three that graphene mass percentage content is 41.1%
First compound blob of viscose of EP rubbers.
Step 2 LiFePO4 machinery is mixed into
The graphene content for weighing step 1 preparation is that the compound blob of viscose 100g of 41.1% ethylene propylene diene rubber is put into operating
In twin rollers roller, roll-in packet roller is gradually added LiFePO 4 powder 123.3g and dioctyl phthalate 20ml, mixing mill
25min is pressed, during which the LiFePO 4 powder trickled down outside roller is all returned to and is mixed into colloid on roller, then beats triangle bag 10
Secondary, thin pass-out piece forms graphene-compound blob of viscose of LiFePO4-rubber；
The charing of the compound blob of viscose of step 3
Step 2 is prepared ethylene propylene diene rubber removing graphene-compound blob of viscose of LiFePO4-rubber to be put into porcelain boat, is put
Enter tube furnace, be passed through nitrogen and heat, control hydrogen flowing quantity 0.2L/min, 15 DEG C/min of heating rate is warming up to 1000 DEG C, protects
Warm 10min, the ethylene propylene diene rubber removing graphene-compound blob of viscose of LiFePO4-rubber for preparing step 2 sufficiently carbonize, shape
At LiFePO4-graphene carbonized foams body；
Step 4 LiFePO4-graphene carbonized foams body grinding distribution
LiFePO4-graphene carbonized foams body prepared by step 3 is put into ball grinder, is 1:4 by pellet mass ratio
Diameter 2mm zirconium oxide abrasive ball is added, in drum's speed of rotation 400rpm, grinds 60min, crosses 200 meshes, lower part of screen is divided into phosphorus
Sour iron lithium-graphene conductive agent active powder, i.e. combination electrode material；
The preparation of step 5 graphene lithium ion battery anode pole piece
6% polyvinylidene fluoride of powder quality is added in the LiFePO4 made from step 4-graphene conductive agent active powder
Powder quality 10%N- methyl pyrrolidone solvent is added in alkene, magnetic agitation 10h, continues to stir 4h, forms uniformly sticky mixing
Sticky mixture material is pressed 15mg/cm by object2On the uniform aluminium foil coated in 16 μ m-thicks, it is put into 120 DEG C of vacuum oven and does
Dry 12h suppresses film forming on double rod film laminators, and cuts and the pole piece of diameter 14mm is made obtains working electrode, puts the electrodes into
4h is recycled in vacuum glove box full of argon gas, it is spare；
The assembling of step 5 graphene fastening lithium ionic cell
It in the vacuum glove box full of argon gas, is positive pole with corresponding positive electrode diaphragm obtained, metal lithium sheet is negative
Pole, 1MLiPF6/ dimethyl carbonate (DMC)+ethylene carbonate (EC)+methyl ethyl carbonate (EMC) (volume ratio 1:1:1) are electricity
Liquid is solved, Celgard2400 microporous polypropylene membrane is the assembling that diaphragm carries out CR2032 type button cell, and assembled battery is put
Enter in copper mold and tightened with pliers, obtains the lithium ion battery that rubber removing graphene is positive conductive material；
The charging-discharging performances test result of the battery different multiplying sees attached list 1
Embodiment 5
The removing of step 1 graphite flake layer
Butadiene-styrene rubber 100g is added in the mixer of 0.2L, and expanded graphite crystal 5.0g is added, is switched on, mixing 3min
Afterwards, it takes out, is transferred to two-roll mill and continues to be kneaded 10min, obtain the fourth that graphene oxide mass percentage content is 4.76%
The compound blob of viscose of benzene rubber.
Step 2 cobalt acid lithium machinery is mixed into
The graphene oxide content for weighing step 1 preparation is that the compound blob of viscose 100g of 4.76% butadiene-styrene rubber is put into operating
In twin rollers roller, roll-in packet roller is gradually added mangaic acid powder for lithium 42.84g and dioctyl phthalate 5ml, mixes roll-in
During which the LiFePO 4 powder trickled down outside roller is all returned to and is mixed into colloid on roller by 12min, then beat triangle bag 10
Secondary, thin pass-out piece forms graphene oxide-compound blob of viscose of cobalt acid lithium-rubber；
The charing of the compound blob of viscose of step 3
Step 2 is prepared butadiene-styrene rubber removing graphene oxide-compound blob of viscose of cobalt acid lithium-rubber to be put into porcelain boat, is put into
Muffle furnace is passed through hydrogen and heats, and controls hydrogen flowing quantity 0.005L/min, and 20 DEG C/min of heating rate is warming up to 500 DEG C, heat preservation
50min, the ethylene propylene diene rubber removing graphene oxide-compound blob of viscose of cobalt acid lithium-rubber for preparing step 2 sufficiently carbonize, oxygen
Graphite alkene is reduced, and forms cobalt acid lithium-graphene carbonized foams body；
Step 4 cobalt acid lithium-graphene carbonized foams body grinding distribution
Cobalt acid lithium-graphene carbonized foams body prepared by step 3 is put into ball grinder, is added by pellet mass ratio for 1:3
Enter diameter 2mm zirconium oxide abrasive ball, in drum's speed of rotation 800rpm, grind 50min, cross 350 meshes, lower part of screen is divided into cobalt acid
Lithium-graphene conductive agent active powder, i.e. combination electrode material；
The preparation of step 5 graphene lithium ion battery anode pole piece
9% polyacrylic acid of powder quality is added in the cobalt acid lithium made from step 4-graphene conductive agent active powder,
Powder quality 6%N is added in magnetic agitation 3h, and dinethylformamide solvent continues to stir 5h, forms uniformly sticky mixture,
Sticky mixture material is pressed into 12mg/cm2On the uniform aluminium foil coated in 16 μ m-thicks, it is put into 120 DEG C of dryings of vacuum oven
12h suppresses film forming on double rod film laminators, and cuts and the pole piece of diameter 14mm is made obtains working electrode, puts the electrodes into and fills
4h is recycled in the vacuum glove box of full argon gas, it is spare；
The assembling of step 6 graphene fastening lithium ionic cell
It in the vacuum glove box full of argon gas, is positive pole with corresponding positive electrode diaphragm obtained, metal lithium sheet is negative
Pole, 1MLiPF6/ dimethyl carbonate (DMC)+ethylene carbonate (EC)+methyl ethyl carbonate (EMC) (volume ratio 1:1:1) are electricity
Liquid is solved, Celgard2400 microporous polypropylene membrane is the assembling that diaphragm carries out CR2032 type button cell, and assembled battery is put
Enter in copper mold and tightened with pliers, obtains the lithium ion battery that rubber removing graphene is positive conductive material；
The charging-discharging performances test result of the battery different multiplying sees attached list 1
Embodiment 6
The removing of step 1 graphite flake layer
Butadiene-styrene rubber 20g and natural rubber 80g is added in the mixer of 0.2L, and expanded graphite crystal 25g is added, it is close
It after refining 5min, takes out, is transferred to two-roll mill and continues to be kneaded 40min, obtaining graphene oxide mass percentage content is 20%
The compound blob of viscose of mixed rubber.
Step 2 LiFePO4 machinery is mixed into
The graphene oxide content for weighing step 1 preparation is the compound blob of viscose 100g of 20% mixed rubber, is put into operating
In twin rollers roller, roll-in packet roller is gradually added LiFePO 4 powder 140g and dioctyl phthalate 30ml, mixes roll-in
During which the LiFePO 4 powder trickled down outside roller is all returned to and is mixed into colloid on roller by 20min, then beat triangle bag 10
Secondary, thin pass-out piece forms graphene oxide-compound blob of viscose of LiFePO4-rubber；
The charing of the compound blob of viscose of step 3
Step 2 is prepared mixed rubber removing graphene oxide-compound blob of viscose of LiFePO4-rubber to be put into porcelain boat, is put
Enter Muffle furnace, be passed through hydrogen and heat, control hydrogen flowing quantity 0.5L/min, 15 DEG C/min of heating rate is warming up to 600 DEG C, heat preservation
20min, the mixed rubber removing graphene oxide-compound blob of viscose of LiFePO4-rubber for preparing step 2 are sufficiently carbonized, are aoxidized
Graphene is reduced, and forms LiFePO4-graphene carbonized foams body；
Step 4 LiFePO4-graphene carbonized foams body grinding distribution
LiFePO4-graphene carbonized foams body prepared by step 3 is put into ball grinder, is 1:3 by pellet mass ratio
Diameter 2mm zirconium oxide abrasive ball is added, in drum's speed of rotation 600rpm, grinds 40min, crosses 300 meshes, lower part of screen is divided into phosphorus
Sour iron lithium-graphene conductive agent active powder, i.e. combination electrode material；
The preparation of step 5 graphene lithium ion battery anode pole piece
10% polyethylene of powder quality is added in the LiFePO4 made from step 4-graphene conductive agent active powder
Powder quality 8%N- methyl pyrrolidone solvent is added in alcohol, magnetic agitation 8h, continues to stir 4h, forms uniformly sticky mixing
Sticky mixture material is pressed 15mg/cm by object2On the uniform aluminium foil coated in 16 μ m-thicks, it is put into 120 DEG C of vacuum oven and does
Dry 12h suppresses film forming on double rod film laminators, and cuts and the pole piece of diameter 14mm is made obtains working electrode, puts the electrodes into
4h is recycled in vacuum glove box full of argon gas, it is spare；
The assembling of step 5 graphene fastening lithium ionic cell
It in the vacuum glove box full of argon gas, is positive pole with corresponding positive electrode diaphragm obtained, metal lithium sheet is negative
Pole, 1MLiPF6/ dimethyl carbonate (DMC)+ethylene carbonate (EC)+methyl ethyl carbonate (EMC) (volume ratio 1:1:1) are electricity
Liquid is solved, Celgard2400 microporous polypropylene membrane is the assembling that diaphragm carries out CR2032 type button cell, and assembled battery is put
Enter in copper mold and tightened with pliers, obtains the lithium ion battery that rubber removing graphene is positive conductive material；
The charging-discharging performances test result of the battery different multiplying sees attached list 1
The charging and discharging capacity test result of 1 battery sample of table
It is added in LiFePO4 from the commercially available graphene of 1 same ratio of embodiment, ground mixing, adhesive is added again
It is fully ground rear solubilizer mix, is coated, drying, after press mold, the anode as lithium ion battery is assembled into button cell, warp
Charging-discharging performances detection, obtains the charge and discharge curve under the conditions of different multiplying；Using LiFePO4 as energy storage activity in contrast table 1
Charge and discharge data under the conditions of the embodiment 1 of object, embodiment 2, embodiment 4, the different multiplying of embodiment 6 can be seen that commercially available
The positive electrode that graphene and LiFePO4 are directly mixed to get, the graphene obtained with the present invention using rubber removing graphite are multiple
Conjunction rubber block is decentralized medium, after being mixed by mechanical strength, in LiFePO4-graphene carbonized foams that high-temperature roasting is formed
The positive electrode that smashed powder is mixed to get is compared, and the big multiplying power charge and discharge curve of 1C is higher than, when especially 5C
Charge and discharge curve is decayed quickly, and 5C charging curve is the 65.1% of 1 sample of embodiment, and discharge performance is 66.9%.
Since the graphene compounded rubber block of rubber removing graphite acquisition is after twin rollers strength mixture operation, keep energy storage living
Property substance LiFePO4 be uniformly mixed into graphene compounded rubber block, being formed mutually interspersed has three-dimensional conductive network knot
The composite foam block particle of structure is fired, is ground up, sieved to obtain visibly homogeneous LiFePO4-graphene energy storage conduction
Agent active matter；And commercially available graphene is due to huge specific surface area, high surface can, and make graphene powder in storage and transportation
Generate agglomeration in the process, from Fig. 1 commercially available graphene penetrate intensity than rubber removing graphene diffracted intensity it is high by 14.9
This phenomenon also sufficiently proves again, the reunion graphene with class non-graphitic state is formed in commercially available graphene, they are difficult to pass through
Simple mechanical mixture is uniformly distributed among the electrical conductive activities substance such as LiFePO4, forms three-dimensional conductive network structure, electricity
Therefore transport factor is obstructed and declines performance, be to influence its big multiplying power charging-discharging performances as cell positive material, especially
It is the key that 5C charge-discharge performance.
Energy storage active matter is mixed with charing black lead alkene conductive agent active powder made from step 3, is added by same method
Enter adhesive magnetic agitation, instills solvent and form uniform grume mixture.By grume mixture even application on copper foil,
Film forming is suppressed in vacuum drying on double rod film laminators, and is cut and the pole piece of diameter 14mm is made is obtained working electrode, and electrode is put
Enter and is used as negative electrode material after recycling in the vacuum glove box full of argon gas；
In addition to CR2032 type button cell, according to the diameter and thickness difference of battery, CR2025 can also be made,
The positive electrode of CR2020, CR2016, CR2450, CR2430 etc.；
Unaccomplished matter of the present invention is well-known technique.
Claims (9)
1. a kind of preparation method of rubber removing graphene combination electrode material, it is characterized in that method includes the following steps:
Step 1: the removing of graphite flake layer
Rubber matrix and graphite raw material are added in mixer, after mixing 3-20min, double rod open mills is transferred to and is kneaded
10-60min obtains the compounded rubber block containing graphene or graphene oxide 4~45%；
Wherein, mass ratio is rubber matrix: graphite raw material=100:5-70；
Step 2: energy storage active substance is mixed into
Upper step is obtained into the twin rollers that compounded rubber block is added in operating, after rolling packet roller, energy storage active powder is added
It with dioctyl phthalate 5-30ml, is kneaded 10-30 minutes, forms graphene-compound film of energy storage active substance-rubber,
Or graphene oxide-compound film of energy storage active substance-rubber；
Wherein, the quality of energy storage active matter is 3-9 times of institute's containing graphene in compounded rubber block or graphene oxide quality；
Step 3: the charing of compounded rubber
Graphene or graphene oxide-energy storage active substance-compounded rubber piece that upper step obtains are put into crucible, covers, puts
It sets in heating equipment, 10~50min of heat preservation roasting, obtains energy storage active substance-graphene carbonized foams at 500~1000 DEG C
Body；
Step 4: energy storage active substance-graphene carbonized foams body grinding distribution
- 350 mesh of 200 mesh will be crossed after energy storage active substance-graphene carbonized foams body grinding, obtains energy storage active substance-stone
Black alkene conductive agent active powder, i.e. combination electrode material.
2. the preparation method of rubber removing graphene combination electrode material as described in claim 1, it is characterized in that the step
Energy storage active substance-graphene carbonized foams body in rapid 4 is ground in mortar ball mill in hand lapping or ball grinder and grinds
Mill, drum's speed of rotation are 400~1000rpm, grind 15~60min, pellet mass ratio 1:2-4, and abrading-ball is the oxidation of diameter 2mm
Zirconium.
3. the preparation method of rubber removing graphene combination electrode material as described in claim 1, it is characterized in that described in step 1
Graphite raw material is crystalline flake graphite, expanded graphite and expansible graphite.
4. the preparation method of rubber removing graphene combination electrode material as described in claim 1, it is characterized in that the rubber
Matrix body includes: natural rubber, butadiene-styrene rubber, ethylene propylene diene rubber, neoprene or nitrile rubber.
5. the preparation method of rubber removing graphene combination electrode material as described in claim 1, it is characterized in that described in step 2
Energy storage active matter refers to LiFePO4, cobalt acid lithium or LiMn2O4.
6. the preparation method of rubber removing graphene combination electrode material as described in claim 1, it is characterized in that described in step 3
Heating equipment includes: the carbonizations such as micro-wave oven, tube furnace, Muffle furnace or vacuum sintering furnace roasting.
7. the preparation method of rubber removing graphene combination electrode material as described in claim 1, it is characterized in that described in step 3
Roasting is carried out under nitrogen or atmosphere of hydrogen；When graphite raw material is crystalline flake graphite, atmosphere is nitrogen；When graphite raw material is expansion
When graphite or expansible graphite, atmosphere is hydrogen；Gas flow is 0.005L/min-5L/min, and the pressure of vacuum drying oven is
0.1pa-100pa。
8. the application of rubber as described in claim 1 removing graphene combination electrode material, with being characterized by graphene button
The assembling of formula lithium ion battery.
9. the application of rubber as described in claim 1 removing graphene combination electrode material, with being characterized by including following step
It is rapid:
(1) it is added adhesive into energy storage active substance-graphene conductive agent active powder, after magnetic agitation 3h-10h, drop
After entering solvent, continue to stir 3h-6h formation grume mixture；By grume mixture even application on aluminium foil, it is put into true
Empty drying box is dry, and film forming is suppressed on double rod film laminators, and cuts and pole piece is made obtains working electrode；
Wherein, adhesive quality is energy storage active matter-graphene conductive agent active powder 5%-10%；The body that solvent is added
The ratio of product (ml) and energy storage active substance-graphene conductive agent active powder quality (g) is 1-4:1；Aluminium foil unit plane
Long-pending coated weight is the amount 5mg/cm of grume mixture2-20mg/cm2；
(2) it in the vacuum glove box full of argon gas, is positive pole with corresponding positive electrode diaphragm obtained, metal lithium sheet is negative
Pole, 1M LiPF6/ dimethyl carbonate (DMC)+ethylene carbonate (EC)+methyl ethyl carbonate (EMC) (volume ratio 1:1:1) are electricity
Liquid is solved, Celgard2400 microporous polypropylene membrane is the assembling that diaphragm carries out different model button cell, and assembled battery is put
Enter in copper mold and tightened with pliers, obtains the lithium ion battery that roasting rubber removing graphene is positive conductive material；
Step 5 described adhesive refers to Kynoar, polyacrylic acid, polyvinyl alcohol, gelatin, one in carboxymethyl cellulose
Kind；
Solvent described in step 5 is n,N-Dimethylformamide, O-phthalic alkanol amides, N-Methyl pyrrolidone and dimethyl
The mixture of one or both of acetamide.
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