CN108933236A - It is a kind of to include graphene/cellulose composite material lithium ion battery and preparation method thereof - Google Patents
It is a kind of to include graphene/cellulose composite material lithium ion battery and preparation method thereof Download PDFInfo
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- CN108933236A CN108933236A CN201710390786.6A CN201710390786A CN108933236A CN 108933236 A CN108933236 A CN 108933236A CN 201710390786 A CN201710390786 A CN 201710390786A CN 108933236 A CN108933236 A CN 108933236A
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- H01M4/02—Electrodes composed of, or comprising, active material
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Abstract
The invention discloses a kind of negative electrode for lithium ion battery, anode and lithium ion battery and preparation method thereof, the cathode includes graphene/cellulose composite material layer on one side surface of negative electrode tab and negative electrode tab；The anode includes graphene/cellulose composite material layer on one side surface of positive plate and positive plate；The graphene/cellulose composite material layer includes graphene and cellulose；The coating can effectively inhibit the growth of cathode pole piece surface dendrite, improve cycle performance of battery and security performance；Pole piece and the direct interface internal resistance of electrolyte can be effectively reduced in the coating, and the capacity of corresponding battery can be improved；The lithium ion battery circulation volume with higher and cyclical stability being prepared using the cathode and/or anode, and there is good circulation safe performance.The preparation method of the lithium ion battery is simple, and reaction condition is mild, and fabrication cycle is short, and the production of heavy industrialization may be implemented.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of to include graphene/cellulose composite material
Lithium ion battery and preparation method thereof.
Background technique
Lithium ion battery relies primarily on lithium ion, and movement carrys out work between a positive electrode and a negative electrode.In charge and discharge process, Li+
Insertion and deintercalation back and forth between two electrodes：When charging, Li+From positive deintercalation, it is embedded in cathode by electrolyte, cathode is in
Lithium-rich state；It is then opposite when electric discharge.
Lithium ion battery generally uses the material for containing elemental lithium as electrode, is the representative of modern high performance battery.Its
With small in size, light-weight, operating voltage is high, specific energy is big, have extended cycle life, be pollution-free the advantages that and by the blueness of researcher
It looks at.Can be widely applied to aerospace, electronic device, daily life every field in.But it is prepared into current technique
The energy density and theoretical capacity of the lithium ion battery arrived are all relatively low, are no longer satisfied the needs of people；Moreover,
After long-time use, lithium metal can crystallize to form dendritic lithium metal on cathode --- dendrite；When the dendritic growth arrives
Diaphragm will be punctured to a certain degree, causes internal short-circuit of battery, seriously threatens personal safety, and this severely limits lithium ion batteries
The extension of service life, the raising of energy density and theoretical capacity.
Currently, mainly having preparation that there is the cathode system of 3 D stereo network structure for the growth of dendrite inhibition, negative
Pole surface increases decorative layer, adds effective auxiliary agent in the electrolytic solution, develops organic and inorganic solid electrolyte, modified existing diaphragm
Increase it to a variety of methods such as the tolerance degree of dendrite, wherein existing negative terminal surface make the method for modification with respect to practicability compared with
Height, operation is more easy, to be widely noticed.The material selection of cathode decorative layer has attracted much attention, and among these includes glass fibre
Etc. various types of materials.Although the material selected at present can effectively reduce the generation of dendrite, to the cycle performance of battery have compared with
It is big to influence, while can also dramatically increase the weight of battery.
Graphene is a kind of new material of individual layer laminated structure being made of carbon atom, is known most thin, most hard
Nano material has ultra-thin, the mechanical strength of superelevation, unique gas barrier, high-specific surface area and surface-active, and has both
The characteristic of common graphite high temperature resistant, corrosion-resistant, high lubrication.0.334 nanometer of single-layer graphene theoretic throat, thermal coefficient is high,
Electron transfer rate is exceedingly fast, and is the minimum material of current resistivity, therefore is expected to can be used to develop thinner, conductive speed faster
Electronic component or transistor of new generation, be our times emphasis research and development and production novel conductive, Heat Conduction Material, future will be wide
It is general to be applied to the industrial circles such as mobile device, aerospace, new energy battery, biological medicine.Nanoscale graphite particulate is to adopt
With special technique, it is aided with vanguard technology and pure Natural Flake Graphite through a long time ground, is centrifuged at a high speed, condensation, pressure
Filter and make, be the new material of high-quality graphene production.
Summary of the invention
In order to solve the deficiencies in the prior art, an object of the present invention is to provide a kind of negative electrode for lithium ion battery, institute
Stating cathode includes graphene/cellulose composite material layer on one side surface of negative electrode tab and negative electrode tab, the graphene/cellulose
Composite layer includes graphene, cellulose and other auxiliary agents.
The second object of the present invention is to provide a kind of lithium ion battery anode, the anode includes positive plate and positive plate
Graphene/cellulose composite material layer on one side surface, the graphene/cellulose composite material layer include graphene, fibre
Dimension element and other auxiliary agents.
The third object of the present invention is to provide a kind of lithium ion battery, and the lithium ion battery includes above-mentioned lithium-ion electric
Pond cathode and/or above-mentioned lithium ion battery anode.
Grapheme material has good electron transport ability in lamella direction, is widely used in all kinds of electronic devices
In research, if it is compound with electrode material, the internal resistance between respective electrode material can be reduced, to improve the charge and discharge of battery
Capacitance, while graphene has good heat-conductive characteristic, phenomena such as heat conduction velocity can be increased, mitigate hot-spot
Appearance, and then increase battery security performance.However, finding in the actual operation process, graphene sheet layer structure is in liquid phase
High concentration dispersion is difficult in system；For researcher by a large amount of experiment discovery, cellulose is that one kind can be good in liquid-phase system
The material dispersed well, meanwhile, also there is the characteristic of high temperature resistant degree.Graphite and cellulose are carried out at ball milling by a certain percentage
Graphene/cellulose composite material can be made in reason, and can be real under the action of cellulose using the processing mode of ball milling
Now to the removing of the graphite number of plies, so that the thinner thickness of the graphite not after oxidation processes, removing obtains graphene, and shells
It can be grafted (or combination) cellulose between obtained graphene layer or surface, so that graphene exists more surely in the slurry
It is fixed.Solubility property is good in water for the composite material simultaneously, by adding a certain amount of inorganic nanoparticles, organic nanometer granule
Or other auxiliary agents, the slurry of higher concentration can be prepared, when being coated on positive and negative anodes pole piece, gained coating and base are bonded
Well, and electrode plates can be effectively reduced to mutual internal resistance in the coating, improve the charge/discharge capacity of corresponding battery.
Cellulose forms two-dimensional network in negative terminal surface simultaneously, and has graphene to inlay wherein it is possible to effectively prevent charge and discharge
Lithium ion prolongs the growth of fixed-direction, the generation of dendrite inhibition in journey.Based on such thinking, the present invention is completed.
The first aspect of the present invention is to provide a kind of negative electrode for lithium ion battery, and the cathode includes negative electrode tab and negative electrode tab
Graphene/cellulose composite material layer on one side surface, the graphene/cellulose composite material layer include graphene, fibre
Dimension element and other auxiliary agents, between the lamella of described cellulose a part insertion graphene, another part be attached to the piece of graphene
Layer surface；Other described auxiliary agents are selected from least one of surfactant, dispersing agent.
According to the present invention, the negative electrode tab with a thickness of 50-150 μm, such as 70 μm, 80 μm, 90 μm, 100 μm, 110 μm,
120μm、130μm、140μm、150μm。
According to the present invention, the negative electrode tab includes negative electrode active material, conductive agent, first binder and negative current collector.
According to the present invention, the negative electrode active material is in natural graphite, carbon nanotube, artificial graphite, graphene
It is at least one.
According to the present invention, the negative current collector is copper foil.
The second aspect of the present invention is to provide a kind of preparation method of above-mentioned negative electrode for lithium ion battery, the method includes
Following steps：
(1) graphite and cellulose are mixed and is ground, mixed material is prepared；
(2) mixed material of step (1) is soluble in water, other auxiliary agents are added, is uniformly mixed, the graphite is prepared
Alkene/cellulose composite material mixed slurry；
(3) mixed slurry of step (2) is coated on one side surface of negative electrode tab；
(4) negative electrode tab for being coated with mixed slurry in step (3) is dried, it is negative that the lithium ion battery use is prepared
Pole；
Wherein, other described auxiliary agents are selected from least one of surfactant, dispersing agent.
According to the present invention, in step (1), the grinding is preferably ground in the ball mill, when the grinding
Between be 5-24h；The grinding temperature is room temperature.
According to the present invention, in step (2), the mass ratio of the mixed material and water is (0.1-50):100, preferably
(0.5-33):100, also preferably (1-15):100.
According to the present invention, in step (3), the coating is selected from modes such as spraying, scraper coating, applicator roll, coating brushs
At least one of.
According to the present invention, it will be understood by those skilled in the art that in step (3), the negative electrode tab is using existing skill
The battery cathode sheet of art manufacture.
Preferably, the battery cathode sheet is made of negative current collector and negative electrode material layer, and the negative electrode material layer includes
Negative electrode active material, conductive agent and first binder.
According to the present invention, in step (4), the time of the drying is 1-24h；The temperature of the drying is 60-120
℃。
The third aspect of the present invention is to provide a kind of lithium ion battery anode, and the anode includes positive plate and positive plate
Graphene/cellulose composite material layer on one side surface, the graphene/cellulose composite material layer include graphene, fibre
Dimension element and other auxiliary agents, between the lamella of described cellulose a part insertion graphene, another part be attached to the piece of graphene
Layer surface；Other described auxiliary agents are selected from least one of surfactant, dispersing agent.
According to the present invention, the positive plate with a thickness of 50-150 μm, such as 70 μm, 80 μm, 90 μm, 100 μm, 110 μm,
120μm、130μm、140μm、150μm。
According to the present invention, the positive plate includes positive electrode active materials, conductive agent, first binder and plus plate current-collecting body.
According to the present invention, the positive electrode active materials are selected from cobalt acid lithium, LiMn2O4, LiFePO4, nickle cobalt lithium manganate, nickel cobalt
At least one of lithium aluminate trielement composite material.
According to the present invention, the plus plate current-collecting body is aluminium foil.
The fourth aspect of the present invention is to provide a kind of preparation method of above-mentioned lithium ion battery anode, the method includes
Following steps：
(a) graphite and cellulose are mixed and is ground, mixed material is prepared；
(b) mixed material step (a) being prepared is soluble in water, other auxiliary agents are added, and is uniformly mixed, is prepared
The mixed slurry of the graphene/cellulose composite material；
(c) mixed slurry of step (b) is coated on one side surface of positive plate；
(d) positive plate for being coated with mixed slurry in step (c) is dried, the lithium ion battery is prepared with just
Pole；
Wherein, other described auxiliary agents are selected from least one of surfactant, dispersing agent.
According to the present invention, in step (a), the grinding is preferably ground in the ball mill, when the grinding
Between be 5-24h；The grinding temperature is room temperature.
According to the present invention, in step (b), the mass ratio of the mixed material and water is (0.1-50):100, preferably
(0.5-33):100, also preferably (1-15):100.
According to the present invention, in step (c), the coating is selected from modes such as spraying, scraper coating, applicator roll, coating brushs
At least one of.
According to the present invention, it will be understood by those skilled in the art that in step (c), the positive plate is using existing skill
The battery positive pole piece of art manufacture.
Preferably, the battery anode slice is made of plus plate current-collecting body and positive electrode material layer, and the positive electrode material layer includes
Positive electrode active materials, conductive agent and first binder.
According to the present invention, in step (d), the time of the drying is 1-24h；The temperature of the drying is 60-120
℃。
In above-mentioned first aspect and the third aspect, the graphene/cellulose composite material layer is by including the following steps
Method obtain：
Graphite and cellulose are mixed and are ground by (1 '), and mixed material is prepared；
(2 ') are soluble in water by the mixed material of step (1 '), other auxiliary agents are added, and are uniformly mixed, the stone is prepared
The mixed slurry of black alkene/cellulose composite material；
The mixed slurry of step (2 ') is coated on one side surface of electrode plates by (3 ')；
(4 ') dry the electrode plates that mixed slurry is coated in step (3 '), are prepared and are attached to the pole piece
Graphene/cellulose composite material layer on one side surface.
According to the present invention, in step (1 '), the grinding is preferably ground in the ball mill, when the grinding
Between be 5-24h；The grinding temperature is room temperature.
According to the present invention, in step (2 '), the mass ratio of the mixed material and water is (0.1-50):100, preferably
(0.5-33):100, also preferably (1-15):100.
According to the present invention, in step (3 '), the coating is selected from modes such as spraying, scraper coating, applicator roll, coating brushs
At least one of.
According to the present invention, in step (4 '), the time of the drying is 1-24h；The temperature of the drying is 60-120
℃。
In above-mentioned first aspect and the third aspect, the conductive agent be selected from acetylene black, conductive carbon black (such as Super P,
Super S, 350G), carbon fiber (VGCF), carbon nanotube (CNTs), Ketjen black (such as KetjenblackEC300J,
KetjenblackEC600JD, Carbon ECP, Carbon ECP600JD), graphite agent (such as KS-6, KS-15, SFG-
At least one of 6, SFG-15).
In above-mentioned first aspect and the third aspect, the first binder is selected from polyvinyl alcohol, polytetrafluoroethylene (PTFE), polyolefin
At least one of class, Kynoar, butadiene-styrene rubber, Viton, polyurethanes, hydroxymethyl cellulose salt.
Above-mentioned first aspect into fourth aspect, the graphite be selected from natural flake graphite, Scaly graphite, micro crystal graphite,
One of synthetic graphite or mixture；The cellulose is selected from one of native cellulose and its derivative and a variety of.
Preferably, the graphite is selected from natural flake graphite；The cellulose is selected from methylcellulose, ethyl cellulose,
Hydroxymethyl cellulose, cellulose acetate, hydroxyethyl cellulose, hydroxypropyl methylcellulose.
According to the present invention, the graphene/cellulose composite material layer is with a thickness of 0.1-30 μm.
According to the present invention, the graphene/cellulose composite material layer coating surface density is 0.2-10g/m2。
According to the present invention, the graphene/cellulose composite material layer includes graphene, cellulose and other auxiliary agents；Institute
The mass ratio for stating graphene and cellulose is (1-70):100, preferably (20-50):100；Other described auxiliary agents and cellulose
Mass ratio is (1-30):100, preferably (5-20):100.
According to the present invention, the dispersing agent in other described auxiliary agents includes castor oil, lauryl sulfate, triethyl group hexyl
It is phosphoric acid, methyl anyl alcohol, polyacrylamide, polyoxyethylene ether, one or more in oleamide.
According to the present invention, the surfactant in other described auxiliary agents includes dodecyl benzene sulfonate, dioctyl succinate
Sour sulfonate, fatty alcohol polyoxyethylene ether, Brij, polyoxyethylene fatty acid ester, oleate, in stearate
It is one or more.
It according to the present invention, further include the second binder in the graphene/cellulose composite material layer.
Preferably, the mass ratio of second binder and cellulose is (0-20):100, preferably (0-15):100.
According to the present invention, second binder includes butadiene-styrene rubber, Viton, polyvinyl alcohol, hydroxymethyl cellulose
Salt, polyacrylic acid, polyacrylate and its derivative, polyacrylonitrile, acrylic ester-acrylonitrile copolymer, polymethylacrylic acid
One of methyl esters, dimethyl-dipropenyl ammonium chloride, alginate, pectate, deer horn glue salt are a variety of.
The fifth aspect of the present invention is to provide a kind of lithium ion battery, and the lithium ion battery includes above-mentioned lithium-ion electric
Pond cathode and/or above-mentioned lithium ion battery anode.
According to the present invention, the lithium ion battery can also include diaphragm.
According to the present invention, the diaphragm include diaphragm base, it is multiple towards graphene/cellulose on one side surface of positive plate
Condensation material layer and/or towards the graphene on one side surface of negative electrode tab/cellulose composite material layer；Graphene/the cellulose
Composite layer includes graphene, cellulose and other auxiliary agents, and described cellulose a part is embedded between the lamella of graphene, is another
A part is attached to the sheet surfaces of graphene；Other described auxiliary agents are selected from least one of surfactant, dispersing agent.
Beneficial effects of the present invention：
1. the cathode includes negative electrode tab and bears the present invention provides a kind of negative electrode for lithium ion battery and preparation method thereof
Graphene/cellulose composite material layer on one side surface of pole piece, the graphene/cellulose composite material layer includes graphite
Alkene, cellulose and other auxiliary agents.The graphene/cellulose composite material layer can be applied by way of being added dropwise or coating
Negative electrode for lithium ion battery piece surface is overlayed on, the coating can effectively inhibit the growth of cathode pole piece surface dendrite, improve electricity
Pond cycle performance and security performance.The preparation method of the negative electrode for lithium ion battery is simple, and reaction condition is mild, fabrication cycle
It is short, the production of heavy industrialization may be implemented.
2. the anode includes one side surface of positive plate and positive plate the present invention provides a kind of anode and preparation method thereof
On graphene/cellulose composite material layer, the graphene/cellulose composite material layer include graphene, cellulose and its
His auxiliary agent；The composite material is that graphite and cellulose are prepared after ball-milling treatment；Graphene/the cellulose is multiple
Pole piece and the direct interface internal resistance of electrolyte can be effectively reduced in condensation material coating, and the capacity of corresponding battery can be improved.
3. the lithium ion battery includes above-mentioned negative electrode of lithium ion battery the present invention provides a kind of lithium ion battery
And/or above-mentioned anode；Lithium ion battery circulation volume with higher and cyclical stability, and there is good circulation
Security performance.
Detailed description of the invention
Fig. 1 is battery first charge-discharge curve graph obtained in embodiment 1.
Fig. 2 is battery different multiplying charge and discharge specific discharge capacity variation diagram obtained in embodiment 1.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than for limiting the scope of the invention.Furthermore, it is to be understood that after having read documented content of the invention, this
Field technical staff can make various changes or modifications the present invention, and such equivalent forms are equally fallen such as protection model of the invention
It encloses.
In the present embodiment, when the lithium ion battery being prepared carries out rate charge-discharge test, the lithium ion
Battery carries out charge and discharge cycles test under 0.1C, 0.5C, 1C, 2C, 5C, 10C different multiplying respectively, records corresponding multiplying power respectively
Lower specific discharge capacity.
In the present embodiment, when the lithium ion battery being prepared carries out heat stability testing, the lithium-ion electric
After pond completes charge and discharge cycles 20 times under 0.1C multiplying power, constant temperature in 140 DEG C of silicone oil bath is placed it in, and monitor battery simultaneously
Open circuit voltage variations situation is recorded in battery open circuit voltage values after 1h.
Embodiment 1
Natural flake graphite 60g and ethyl cellulose 100g are sufficiently mixed by step 1), and ball milling 5h at room temperature
Obtain composite graphite alkene cellulosic material powder；
Neopelex 25g is dissolved in 460mL water by step 2), then the resulting graphene fiber of step 1) is plain
Material 160g is dissolved in above-mentioned water, is sufficiently stirred, and graphene/cellulose composite mortar is made；
The preparation of step 3) anode
The preparation of positive plate：By 85 parts of positive active material cobalt acid lithium, 5 parts of acetylene black, 5 parts of electrically conductive graphite, PVDF5 parts of use
N-Methyl pyrrolidone is sufficiently mixed to obtain anode sizing agent, is evenly applied to aluminum foil current collector surface, completes the preparation of positive plate；
The resulting graphene of step 2)/cellulose composite mortar is coated on above-mentioned anode electrode pole piece and vacuum
120 DEG C of drying 10h are prepared described comprising graphene/cellulose composite material negative electrode pole piece, wherein graphite
Alkene/cellulose mixed slurry coating is with a thickness of 15 μm；
The preparation of step 4) battery cathode
The preparation of negative electrode tab：By 87 parts of negative electrode active material electrically conductive graphite, 5 parts of acetylene black, sodium cellulose glycolate (as
First binder) 5 parts, 3 parts of butadiene-styrene rubber (as first binder) be sufficiently mixed to obtain cathode slurry with alcohol-water mixed solution
Material, is evenly applied to copper foil current collector surface, completes the preliminary preparation of negative electrode tab；
The resulting graphene of step 2)/cellulose composite mortar is coated on above-mentioned negative electrode pole piece and vacuum
120 DEG C of drying 10h are prepared described comprising graphene/cellulose composite material negative electrode pole piece, wherein graphite
Alkene/cellulose mixed slurry coating is with a thickness of 28 μm；
Step 5) battery assembly
It is put into polypropylene diaphragm among cathode pole piece obtained in the anode obtained in step 3) and step 4), quotient is added
With 100 μ L of lithium-ion battery electrolytes, it is put into hydraulic sealing machine sealing after reed, prepares button-shaped 2032 lithium ion battery；
Step 6) carries out rate charge-discharge test and heat stability testing.
Embodiment 2
Embodiment 1 is repeated, difference is：
Natural flake graphite 30g and ethyl cellulose 100g are sufficiently mixed by step 1), and ball milling 5h at room temperature
Obtain composite graphite alkene cellulosic material powder；
Methyl anyl alcohol 15g is dissolved in 1500mL water by step 2), then by the resulting graphene fiber cellulosic material of step 1)
145g is dissolved in above-mentioned water, is sufficiently stirred, and graphene/cellulose composite mortar is made；
In step 3), the mixed slurry coating of the positive electrode surface with a thickness of 0.5 μm；
In step 4), the mixed slurry coating of the negative terminal surface with a thickness of 1 μm；
Embodiment 3
Embodiment 1 is repeated, difference is：
Scaly graphite 10g and ethyl cellulose 100g are sufficiently mixed by step 1), and ball milling 5h at room temperature, can be obtained
Composite graphite alkene cellulosic material powder；
Lauryl sodium sulfate 0.3g is dissolved in 3700mL water by step 2), then the resulting graphene fiber of step 1) is plain
Material 11g is dissolved in above-mentioned water, is sufficiently stirred, and graphene/cellulose composite mortar is made；
In step 3), anode electrode pole piece is not coated by mixed slurry.
Embodiment 4
Embodiment 1 is repeated, difference is：
Natural flake graphite 15g and cellulose acetate 100g are sufficiently mixed by step 1), and ball milling 5h at room temperature
Obtain composite graphite alkene cellulosic material powder；
Polyoxyethylene ether 0.4g is dissolved in 2000mL water by step 2), then by the resulting graphene fiber cellulosic material of step 1)
12g is dissolved in above-mentioned water, is sufficiently stirred, and graphene/cellulose composite mortar is made；
In step 4), negative electrode pole piece is not coated by mixed slurry.
Embodiment 5
Embodiment 1 is repeated, difference is：
Natural flake graphite 25g and hydroxyethyl cellulose 100g are sufficiently mixed by step 1), and ball milling 5h at room temperature, i.e.,
Composite graphite alkene cellulosic material powder can be obtained；
Neopelex 18g is dissolved in 715mL water by step 2), then the resulting graphene fiber of step 1) is plain
Material 143g is dissolved in above-mentioned water, is sufficiently stirred, and graphene/cellulose composite mortar is made；
In step 3), cobalt acid lithium is replaced with into LiMn2O4；
Embodiment 6
Embodiment 1 is repeated, difference is：
Natural flake graphite 55g and hydroxypropyl methylcellulose 100g are sufficiently mixed by step 1), and ball milling 5h at room temperature, i.e.,
Composite graphite alkene cellulosic material powder can be obtained；
Triethyl group hexyl phosphoric acid 20g is dissolved in 500mL water by step 2), then by the resulting graphene fiber material of step 1)
Material 175g is dissolved in above-mentioned water, is sufficiently stirred, and graphene/cellulose composite mortar is made；
In step 4), cobalt acid lithium is replaced with into lithium titanate；
Embodiment 7
Embodiment 1 is repeated, difference is：
Neopelex 25g is dissolved in 460mL water by step 2), then by step (1) resulting graphene fiber
Cellulosic material 160g is dissolved in above-mentioned water, and 5g butadiene-styrene rubber is added, is sufficiently stirred, and graphene/cellulose composite mortar is made；
Comparative example 1
Embodiment 1 is repeated, difference is, the positive cathode for the battery being prepared does not coat.
The performance of lithium ion battery parameter that table 1 is embodiment 1-7 and comparative example 1 is prepared
Fig. 1 is the battery first charge-discharge curve graph that embodiment 1 obtains.As seen from the figure, described to be coated with graphene/fiber
The anode and/or cathode of plain composite layer in lithium ion battery, battery can normal charge and discharge, and battery have compared with
High charge-discharge specific capacity.
Fig. 2 is the battery rate charge-discharge specific discharge capacity variation diagram that embodiment 1 obtains.As seen from the figure, described to be coated with
Graphene/cellulose composite material layer anode and/or cathode are in lithium ion battery, battery to be compared with high power charging-discharging
When, it still can keep higher specific discharge capacity.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of negative electrode for lithium ion battery, which is characterized in that the cathode includes on one side surface of negative electrode tab and negative electrode tab
Graphene/cellulose composite material layer, the graphene/cellulose composite material layer include graphene, cellulose and other help
Agent, between the lamella of described cellulose a part insertion graphene, another part be attached to the sheet surfaces of graphene；It is described its
He is selected from least one of surfactant, dispersing agent by auxiliary agent.
2. negative electrode for lithium ion battery according to claim 1, which is characterized in that the negative electrode tab with a thickness of 50-150
μm, such as 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm.
Preferably, the negative electrode tab includes negative electrode active material, conductive agent, first binder and negative current collector.
Preferably, the negative electrode active material is selected from least one of natural graphite, carbon nanotube, artificial graphite, graphene.
Preferably, the conductive agent is selected from acetylene black, conductive carbon black (such as Super P, Super S, 350G), carbon fiber
(VGCF), carbon nanotube (CNTs), Ketjen black (such as KetjenblackEC300J, KetjenblackEC600JD, Carbon
ECP, Carbon ECP600JD), at least one of graphite agent (such as KS-6, KS-15, SFG-6, SFG-15).
Preferably, the first binder is selected from polyvinyl alcohol, polytetrafluoroethylene (PTFE), polyolefins, Kynoar, butylbenzene rubber
At least one of glue, Viton, polyurethanes, hydroxymethyl cellulose salt.
Preferably, the negative current collector is copper foil.
3. the preparation method of negative electrode for lithium ion battery of any of claims 1 or 2, which is characterized in that the method includes such as
Lower step：
(1) graphite and cellulose are mixed and is ground, mixed material is prepared；
(2) mixed material of step (1) is soluble in water, other auxiliary agents are added, be uniformly mixed, be prepared the graphene/
The mixed slurry of cellulose composite material；
(3) mixed slurry of step (2) is coated on one side surface of negative electrode tab；
(4) negative electrode tab for being coated with mixed slurry in step (3) is dried, the negative electrode for lithium ion battery is prepared；
Wherein, other described auxiliary agents are selected from least one of surfactant, dispersing agent.
Preferably, in step (1), the grinding is preferably ground in the ball mill, and the milling time is 5-
24h；The grinding temperature is room temperature.
Preferably, in step (2), the mass ratio of the mixed material and water is (0.1-50):100, preferably (0.5-33):
100, also preferably (1-15):100.
Preferably, described to coat in the modes such as spraying, scraper coating, applicator roll, coating brush at least in step (3)
It is a kind of.
Preferably, the battery cathode sheet is made of negative current collector and negative electrode material layer, and the negative electrode material layer includes cathode
Active material, conductive agent and first binder.
Preferably, in step (4), the time of the drying is 1-24h；The temperature of the drying is 60-120 DEG C.
4. a kind of lithium ion battery anode, which is characterized in that the anode includes on one side surface of positive plate and positive plate
Graphene/cellulose composite material layer, the graphene/cellulose composite material layer include graphene, cellulose and other help
Agent, between the lamella of described cellulose a part insertion graphene, another part be attached to the sheet surfaces of graphene；It is described its
He is selected from least one of surfactant, dispersing agent by auxiliary agent.
5. lithium ion battery according to claim 4 anode, which is characterized in that the positive plate with a thickness of 50-150
μm, such as 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm.
Preferably, the positive plate includes positive electrode active materials, conductive agent, first binder and plus plate current-collecting body.
Preferably, the positive electrode active materials are selected from cobalt acid lithium, LiMn2O4, LiFePO4, nickle cobalt lithium manganate, nickel cobalt lithium aluminate three
At least one of first composite material.
Preferably, the conductive agent is selected from acetylene black, conductive carbon black (such as Super P, Super S, 350G), carbon fiber
(VGCF), carbon nanotube (CNTs), Ketjen black (such as KetjenblackEC300J, KetjenblackEC600JD, Carbon
ECP, Carbon ECP600JD), at least one of graphite agent (such as KS-6, KS-15, SFG-6, SFG-15).
Preferably, the first binder is selected from polyvinyl alcohol, polytetrafluoroethylene (PTFE), polyolefins, Kynoar, butylbenzene rubber
At least one of glue, Viton, polyurethanes, hydroxymethyl cellulose salt.
Preferably, the plus plate current-collecting body is aluminium foil.
6. the preparation method of lithium ion battery anode described in claim 4 or 5, described method includes following steps：
(a) graphite and cellulose are mixed and is ground, mixed material is prepared；
(b) mixed material step (a) being prepared is soluble in water, other auxiliary agents are added, and is uniformly mixed, and is prepared described
Graphene/cellulose composite material mixed slurry；
(c) mixed slurry of step (b) is coated on one side surface of positive plate；
(d) positive plate for being coated with mixed slurry in step (c) is dried, the lithium ion battery anode is prepared；
Wherein, other described auxiliary agents are selected from least one of surfactant, dispersing agent.
Preferably, in step (a), the grinding is preferably ground in the ball mill, and the milling time is 5-
24h；The grinding temperature is room temperature.
Preferably, in step (b), the mass ratio of the mixed material and water is (0.1-50):100, preferably (0.5-33):
100, also preferably (1-15):100.
Preferably, described to coat in the modes such as spraying, scraper coating, applicator roll, coating brush at least in step (c)
It is a kind of.
Preferably, the battery anode slice is made of plus plate current-collecting body and positive electrode material layer, and the positive electrode material layer includes anode
Active material, conductive agent and first binder.
Preferably, in step (d), the time of the drying is 1-24h；The temperature of the drying is 60-120 DEG C.
7. negative electrode for lithium ion battery according to claim 1 or 2 or lithium ion battery described in claim 4 or 5 are used
Anode, which is characterized in that the graphene/cellulose composite material layer passes through the method included the following steps and obtains：
Graphite and cellulose are mixed and are ground by (1 '), and mixed material is prepared；
(2 ') are soluble in water by the mixed material of step (1 '), other auxiliary agents are added, and are uniformly mixed, the graphite is prepared
Alkene/cellulose composite material mixed slurry；
The mixed slurry of step (2 ') is coated on one side surface of electrode plates by (3 ')；
(4 ') dry the electrode plates that mixed slurry is coated in step (3 '), and the side for being attached to the pole piece is prepared
Graphene/cellulose composite material layer on surface.
Preferably, in step (1 '), the grinding is preferably ground in the ball mill, and the milling time is 5-
24h；The grinding temperature is room temperature.
Preferably, in step (2 '), the mass ratio of the mixed material and water is (0.1-50):100, preferably (0.5-
33):100, also preferably (1-15):100.
Preferably, described to coat in the modes such as spraying, scraper coating, applicator roll, coating brush at least in step (3 ')
It is a kind of.
Preferably, in step (4 '), the time of the drying is 1-24h；The temperature of the drying is 60-120 DEG C.
8. negative electrode for lithium ion battery according to claim 1-7 or lithium ion battery anode or lithium-ion electric
The preparation method of preparation method or the lithium ion battery anode of pond cathode, which is characterized in that the graphite is selected from natural squama
One of piece graphite, Scaly graphite, micro crystal graphite, synthetic graphite or mixture；The cellulose be selected from native cellulose and
One of its derivative and a variety of.
Preferably, the graphite is selected from natural flake graphite；The cellulose is selected from methylcellulose, ethyl cellulose, hydroxyl first
Base cellulose, cellulose acetate, hydroxyethyl cellulose, hypromellose.
Preferably, the graphene/cellulose composite material layer is with a thickness of 0.1-30 μm.
Preferably, the graphene/cellulose composite material layer coating surface density is 0.2-10g/m2。
Preferably, the graphene/cellulose composite material layer includes graphene, cellulose and other auxiliary agents；The graphene
Mass ratio with cellulose is (1-70):100, preferably (20-50):100；The mass ratio of other described auxiliary agents and cellulose is
(1-30):100, preferably (5-20):100.
Preferably, the dispersing agent in other described auxiliary agents includes castor oil, lauryl sulfate, triethyl group hexyl phosphoric acid, first
It is base amylalcohol, polyacrylamide, polyoxyethylene ether, one or more in oleamide.
Preferably, the surfactant in other described auxiliary agents include dodecyl benzene sulfonate, dioctyl succinate acid sulfonate,
One of fatty alcohol polyoxyethylene ether, Brij, polyoxyethylene fatty acid ester, oleate, stearate are more
Kind.
It preferably, further include the second binder in the graphene/cellulose composite material layer.
Preferably, the mass ratio of second binder and cellulose is (0-20):100, preferably (0-15):100.
Preferably, second binder includes butadiene-styrene rubber, Viton, polyvinyl alcohol, hydroxymethyl cellulose salt, polypropylene
Acid, polyacrylate and its derivative, polyacrylonitrile, acrylic ester-acrylonitrile copolymer, polymethyl methacrylate, diformazan
One of base dipropenyl ammonium chloride, alginate, pectate, deer horn glue salt are a variety of.
9. a kind of lithium ion battery, which is characterized in that the lithium ion battery includes lithium-ion electric of any of claims 1 or 2
Pond cathode and/or lithium ion battery described in claim 4 or 5 anode.
10. lithium ion battery according to claim 9, which is characterized in that the lithium ion battery can also include diaphragm.
Preferably, the diaphragm includes diaphragm base, towards the graphene on one side surface of positive plate/cellulose composite material layer
And/or towards the graphene on one side surface of negative electrode tab/cellulose composite material layer；Graphene/the cellulose composite material
Layer includes graphene, cellulose and other auxiliary agents, and described cellulose a part is embedded between the lamella of graphene, another part is attached
Graphene sheet surfaces；Other described auxiliary agents are selected from least one of surfactant, dispersing agent.
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