CN108933216A - It is a kind of to include graphene/cellulose composite material diaphragm and preparation method thereof - Google Patents
It is a kind of to include graphene/cellulose composite material diaphragm and preparation method thereof Download PDFInfo
- Publication number
- CN108933216A CN108933216A CN201710392500.8A CN201710392500A CN108933216A CN 108933216 A CN108933216 A CN 108933216A CN 201710392500 A CN201710392500 A CN 201710392500A CN 108933216 A CN108933216 A CN 108933216A
- Authority
- CN
- China
- Prior art keywords
- graphene
- diaphragm
- cellulose
- composite material
- cellulose composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Include graphene/cellulose composite material diaphragm and preparation method thereof the invention discloses a kind of, the diaphragm includes diaphragm base, towards the graphene in the diaphragm substrate surface of positive plate side/cellulose composite material layer and/or towards the graphene in the diaphragm substrate surface of negative electrode tab side/cellulose composite material layer, and the graphene/cellulose composite material layer includes graphene, cellulose and other auxiliary agents；It is described comprising graphene/cellulose composite material diaphragm in use, not only there is low thickness, high liquid absorption amount, low-resistance characteristic, make capacity of lithium ion battery height, long service life performance, wherein graphene ingredient can also be effectively formed heat transmission network, heat is spread in time when superheating phenomenon locally occurs, to improve diaphragm heat resistance, increase the security performance of battery.The preparation method of the diaphragm 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
Diaphragm and preparation method thereof.
Background technique
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.Lithium ion battery one used at present
As be all composed of positive and negative electrodes, electrolyte and separator.Diaphragm is the key that one of layer assembly in lithium ion battery, lithium ion battery
Relying primarily on lithium ion, movement carrys out work between a positive electrode and a negative electrode.In charge and discharge process, Li+It is round-trip between two electrodes
Insertion and deintercalation, that is, when charging, Li+From positive deintercalation, it is embedded in cathode by electrolyte, cathode is in lithium-rich state；When electric discharge
It is then opposite.And the major function of diaphragm is isolation positive and negative anodes and electronics is prevented to pass through, while can allow for passing through for lithium ion, from
And complete the quick transmission in lithium ion in charge and discharge process between positive and negative anodes.
Currently, common diaphragm is the diaphragm of multilayered structure or ceramics coating in lithium ion battery；It can be played well
The effect for blocking positive and negative pole material and support, starts that local pyrexia can occur when diaphragm is punctured, and septum barrier layer is such as at this time
Fruit can quickly occur to melt closed pore, can walk and explode to avoid battery thermal explosion, but when the electrothermal calefactive rate of part is greater than fusing speed
When spending, it is just unable to reach blocking effect.Moreover, lithium metal can crystallize on cathode and form dendritic gold after long-time use
Belong to lithium --- dendrite；When the dendritic growth will puncture diaphragm to a certain extent, internal short-circuit of battery is caused, people is seriously threatened
Body safety, this severely limits the raisings of the extension of lithium ion battery service life, energy density and theoretical capacity.
Moreover, the energy density and actual capacity for the lithium ion battery being prepared with current technique are all relatively
It is low, be no longer satisfied the needs of people；The superiority and inferiority for being primarily due to membrane properties directly affects the internal resistance of cell, electric discharge
The security performance that capacity, service life cycle and battery use, thus, lithium ion battery is manufactured to the one of diaphragm material product
Cause property require it is high, other than thickness, superficial density, mechanical property these basic demands, size to diaphragm micro-hole and point
The homogeneity of cloth also has very high requirement.
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 multiple comprising graphene/cellulose
Diaphragm of condensation material and preparation method thereof, the diaphragm include diaphragm base, towards graphene/fiber on a positive side surface
Plain composite layer and/or towards the graphene on one side surface of cathode/cellulose composite material layer.
The second object of the present invention is to provide a kind of lithium ion battery, the battery includes above-mentioned diaphragm.
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；And needing to add binder with diaphragm compound tense can just be such that composite construction is stabilized, this
It will lead to greatly increasing for graphene composite diaphragm production difficulty.For researcher by a large amount of experiment discovery, cellulose is one
Kind can in the material of liquid-phase system fine dispersion, meanwhile, also there is the characteristic of high temperature resistant degree.Graphite and cellulose are pressed one
Certainty ratio carries out ball-milling treatment, graphene/cellulose composite material can be made, and using the processing mode of ball milling, in fibre
Under the action of dimension element, the removing to the graphite number of plies can be realized, so that the thinner thickness of the graphite not after oxidation processes,
Removing obtains graphene, and between the graphene layer that removing obtains or surface can be grafted (or combination) cellulose, so that graphite
Alkene exists more stable in the slurry.Solubility property is good in water for the composite material simultaneously, can prepare the slurry of higher concentration,
When being coated on diaphragm substrate surface, gained coating bonds well in substrate surface.Based on above-mentioned thinking, this hair is completed
It is bright.
The first aspect of the present invention is to provide a kind of comprising graphene/cellulose composite material diaphragm, the diaphragm packet
Include diaphragm base, towards graphene/cellulose composite material layer in positive side diaphragm substrate surface and/or towards cathode one
Graphene/cellulose composite material layer in the diaphragm substrate surface of side, the graphene/cellulose composite material layer includes graphite
Alkene, cellulose and other auxiliary agents, described cellulose a part is embedded between the lamella of graphene, another part is attached to graphene
Sheet surfaces；Other described auxiliary agents are selected from least one of surfactant, dispersing agent.
According to the present invention, the diaphragm with a thickness of 5-100 μm, preferably 10-60 μm, for example, 10 μm, 20 μm, 30 μm,
40μm、50μm、60μm。
According to the present invention, the diaphragm base be selected from polypropylene, polyethylene, polyvinylidene fluoride-hexafluoropropylene copolymer,
The multilayer that the single-layer septum or two or more materials that one of polyester, glass fibre, aramid fiber, polyimides material is constituted are constituted
Diaphragm.
According to the present invention, the diaphragm base with a thickness of 2-90 μm, preferably 10-50 μm, such as 10 μm, 20 μm, 30 μ
m、40μm、50μm。
According to the present invention, the graphene/cellulose composite material layer is with a thickness of 0.1-10 μm, for example, 0.5 μm, 1 μm,
2μm、3μm、4μm、5μm、6μm、8μm、10μm。
According to the present invention, the porosity of the diaphragm base is 30%-70%.
According to the present invention, the graphene/cellulose composite material layer passes through the method included the following steps and obtains：
(a) graphite and cellulose are mixed and is ground, mixed material is prepared；
(b) mixed material of step (a) is soluble in water, other auxiliary agents are added, is uniformly mixed, the graphite is prepared
Alkene/cellulose composite material mixed slurry；
(c) mixed slurry of step (b) is coated on the one or both sides surface of the diaphragm base；
(d) diaphragm for being coated with mixed slurry in step (c) is dried, is prepared and is attached to the one of the diaphragm base
Graphene/cellulose composite material layer on side or both side surface；
Wherein, other described auxiliary agents are selected from least one of surfactant, dispersing agent.
The second aspect of the present invention is to provide the above-mentioned preparation method comprising graphene/cellulose composite material diaphragm,
Described 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 the one or both sides surface of diaphragm base；
(4) the diaphragm base that mixed slurry is coated in step (3) is dried, that is, be prepared it is described comprising graphene/
The diaphragm of cellulose composite material；
Wherein, other described auxiliary agents are selected from least one of surfactant, dispersing agent.
According to the present invention, in step (a) or step (1), the grinding is preferably ground in the ball mill, institute
Stating milling time is 5-24h；The grinding temperature is room temperature.
According to the present invention, in step (b) or 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 (c) or step (3), the coating is selected from spraying, scraper coating, applicator roll, coating
At least one of modes such as brush.
According to the present invention, in step (d) or step (4), the time of the drying is 1-24h；The temperature of the drying
It is 30-80 DEG C.
In above-mentioned first aspect and second 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 0.1-10 μm.
According to the present invention, the graphene/cellulose composite material layer coating surface density is 0.2-5g/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 (2-20):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 binder in the graphene/cellulose composite material layer.
Preferably, the mass ratio of the binder and cellulose is (0-10):100, preferably (0-5):100.
According to the present invention, the binder includes butadiene-styrene rubber, Viton, polyvinyl alcohol, hydroxymethyl cellulose salt, gathers
Acrylic acid, polyacrylate and its derivative, polyacrylonitrile, acrylic ester-acrylonitrile copolymer, polymethyl methacrylate,
One of dimethyl-dipropenyl ammonium chloride, alginate, pectate, deer horn glue salt are a variety of.
The third aspect of the present invention is to provide a kind of lithium ion battery, and the lithium ion battery includes above-mentioned diaphragm.
Preferably, the lithium ion battery is at least one of button cell, Stackable batteries, coiled battery.
Preferably, the outer packing of the lithium ion battery is that flexible packaging or steel shell are packed.
Beneficial effects of the present invention：
1. the present invention provides a kind of comprising graphene/cellulose composite material diaphragm and preparation method thereof, it is described every
Film includes diaphragm base, towards the graphene in the diaphragm substrate surface of positive plate side/cellulose composite material layer and/or direction
Graphene/cellulose composite material layer in the diaphragm substrate surface of negative electrode tab side, the graphene/cellulose composite material layer
Including graphene, cellulose and other auxiliary agents；Described cellulose a part is embedded between the lamella of graphene, another part adheres to
In the sheet surfaces of graphene；Other described auxiliary agents are selected from least one of surfactant, dispersing agent.The graphene/
Cellulose composite material layer is that diaphragm substrate surface can be coated in by way of being added dropwise or coating, and is not necessarily in coating procedure
The bonding of the diaphragm base and composite material can be realized by adding binder or only adding a small amount of binder, and described viscous
It is very good to tie effect；Moreover, influence of the binder to diaphragm porosity can also be substantially reduced, is mentioned for the transmission of lithium ion
For effective channel, internal resistance is reduced, increases battery charging and discharging cycle performance；Described includes graphene/cellulose composite material
Diaphragm in use, not only there is low thickness, high liquid absorption amount, low-resistance characteristic, make that capacity of lithium ion battery is high, makes
With service life long performance, wherein graphene ingredient can also be effectively formed heat transmission network, locally occur superheating phenomenon when and
When spread heat, to improve diaphragm heat resistance, increase the security performance of battery.The preparation method of the diaphragm is simple, reaction
Mild condition, fabrication cycle is short, and the production of heavy industrialization may be implemented.
2. the present invention provides a kind of batteries including above-mentioned diaphragm；The battery has good during charge and discharge cycles
Good stability, and at charging and discharging currents larger (10C), it still can maintain higher specific discharge capacity.In addition, circulation one
After the section time, battery is placed at 140 DEG C, it is observed that the open-circuit voltage of battery does not occur significant change after 1h, shows electricity
Pond can still stablize use when heated, i.e. battery has good 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.
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 positive plate preparation.
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 bonding
5 parts of agent, 3 parts of butadiene-styrene rubber binder be sufficiently mixed to obtain negative electrode slurry with alcohol-water mixed solution, be evenly applied to copper foil collection
Flow surface completes negative electrode tab preparation.
Embodiment 1
Natural flake graphite 60g and methylcellulose 100g are sufficiently mixed by step 1), and ball milling 15h at room temperature, i.e.,
Composite graphite alkene cellulosic material powder can be obtained；
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, is sufficiently stirred, and graphene fiber element mixed slurry is made；
The mixed slurry scraper of step 2) is coated to the side of polypropylene diaphragm base by step 3)；
Step 4) will be coated with diaphragm base 40 DEG C of drying 2h in a vacuum drying oven of mixed slurry in step 3), prepare
It obtains described comprising graphene/cellulose composite material diaphragm；The graphene/cellulose composite material coating with a thickness of
2μm。
Step 5) the lithium ion battery assembling：
It is put into graphene/cellulose composite material diaphragm that step 4) obtains among positive electrode and negative electrode pole piece, will apply
100 μ L of commercial li-ion battery electrolyte is added towards cathode side in layer direction, is put into hydraulic sealing machine sealing after reed, system
Standby 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 4), the graphene/cellulose composite material coating is with a thickness of 8 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 by step (1) resulting graphene fiber
Cellulosic material 11g is dissolved in above-mentioned water, is sufficiently stirred, and graphene/cellulose composite mortar is made；
In step 5), the positive side of coating direction direction.
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 material of step (1)
Material 12g is dissolved in above-mentioned water, is sufficiently stirred, and graphene/cellulose composite mortar is made；
In step 4), the graphene/cellulose composite material coating is with a thickness of 8 μm.
In step 5), the positive side of coating direction direction.
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 by step (1) resulting graphene fiber
Cellulosic material 143g is dissolved in above-mentioned water, is sufficiently stirred, and graphene/cellulose composite mortar is made；
In step 3), the mixed slurry applicator roll of step 2) is coated to the bilateral of polypropylene diaphragm base；
In step 4), graphene/cellulose composite material coating thickness of diaphragm base bilateral is 2 μm.
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；
Liver sodium taurocholate 20g is dissolved in 500mL water by step 2), then by the resulting graphene fiber cellulosic material of step (1)
175g is dissolved in above-mentioned water, is sufficiently stirred, and graphene/cellulose composite mortar is made；
In step 3), the mixed slurry applicator roll of step 2) is coated to the bilateral of polypropylene diaphragm base；
In step 4), graphene/cellulose composite material coating thickness of diaphragm base bilateral is 5 μm.
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 1g butadiene-styrene rubber binder is added, is sufficiently stirred, and graphene/cellulose composite pulp is made
Material.
Comparative example 1
Lithium ion battery assembling：
It is put into the polypropylene diaphragm of uncoated graphene/cellulose composite material among positive electrode and negative electrode pole piece, is added
100 μ L of commercial li-ion battery electrolyte is put into hydraulic sealing machine sealing after reed, prepares button-shaped 2032 lithium ion battery,
Carry out rate charge-discharge test and heat stability testing.
Embodiment 1-7 and comparative example 1 are tested by above-mentioned test method, obtain battery performance parameter such as 1 institute of table
Show.
Table 1 is that performance of lithium ion battery parameter is prepared in embodiment 1-7 and comparative example 1
Fig. 1 is the battery first charge-discharge curve graph that embodiment 1 obtains.As seen from the figure, the slurry is used for lithium-ion electric
Chi Zhong, 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, the slurry is used
In lithium ion battery, battery still can keep higher specific discharge capacity when compared with high power charging-discharging.
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 include graphene/cellulose composite material diaphragm, which is characterized in that the diaphragm includes diaphragm base, court
Graphene/cellulose composite material layer in positive side diaphragm substrate surface and/or towards cathode side diaphragm base table
Graphene/cellulose composite material layer on face, the graphene/cellulose composite material layer include graphene, cellulose and
Other auxiliary agents, between the lamella of described cellulose a part insertion graphene, another part be attached to the sheet surfaces of graphene；
Other described auxiliary agents are selected from least one of surfactant, dispersing agent.
2. diaphragm according to claim 1, which is characterized in that the diaphragm with a thickness of 5-100 μm, preferably 10-60 μ
M, such as 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm.
3. diaphragm according to claim 1 or 2, which is characterized in that the diaphragm base is selected from polypropylene, polyethylene, gathers
One of vinylidene difluoride-hexafluoropropylene copolymer, polyester, glass fibre, aramid fiber, polyimides material constitute single layer every
The laminated diaphragm that film or two or more materials are constituted.
Preferably, the diaphragm base with a thickness of 2-90 μm, preferably 10-50 μm, for example, 10 μm, 20 μm, 30 μm, 40 μm,
50μm。
Preferably, the graphene/cellulose composite material layer is with a thickness of 0.1-10 μm, for example, 0.5 μm, 1 μm, 2 μm, 3 μm,
4μm、5μm、6μm、8μm、10μm。
Preferably, the porosity of the diaphragm base is 30%-70%.
4. diaphragm according to claim 1-3, which is characterized in that the graphene/cellulose composite material layer
It is obtained by the method included the following steps：
(a) graphite and cellulose are mixed and is ground, mixed material is prepared；
(b) mixed material of step (a) is soluble in water, other auxiliary agents are added, be uniformly mixed, be prepared the graphene/
The mixed slurry of cellulose composite material；
(c) mixed slurry of step (b) is coated on the one or both sides surface of the diaphragm base；
(d) by step (c) be coated with mixed slurry diaphragm dry, be prepared the side for being attached to the diaphragm base or
Graphene/cellulose composite material layer in both side surface；
Wherein, other described auxiliary agents are selected from least one of surfactant, dispersing agent.
5. the described in any item preparation methods comprising graphene/cellulose composite material diaphragm of claim 1-4, feature
It is, described 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, be uniformly mixed, be prepared the graphene/
The mixed slurry of cellulose composite material；
(3) mixed slurry of step (2) is coated on the one or both sides surface of diaphragm base；
(4) the diaphragm base for being coated with mixed slurry in step (3) is dried, that is, be prepared described comprising graphene/fiber
The diaphragm of plain composite material；
Wherein, other described auxiliary agents are selected from least one of surfactant, dispersing agent.
6. preparation method described in diaphragm according to claim 4 or claim 5, which is characterized in that in step (a) or
In step (1), the grinding is preferably ground in the ball mill, and the milling time is 5-24h；The grinding temperature
For room temperature.
Preferably, in step (b) or 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, in step (c) or step (3), the coating is selected from modes such as spraying, scraper coating, applicator roll, coating brushs
At least one of.
Preferably, in step (d) or step (4), the time of the drying is 1-24h；The temperature of the drying is 30-80
℃。
7. diaphragm according to claim 1-6 or preparation method, 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, hydroxypropyl methylcellulose.
Preferably, the graphene/cellulose composite material layer is with a thickness of 0.1-10 μm.
Preferably, the graphene/cellulose composite material layer coating surface density is 0.2-5g/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 (2-20):100.
8. diaphragm according to claim 1-7 or preparation method, which is characterized in that point in other described auxiliary agents
Powder include castor oil, lauryl sulfate, triethyl group hexyl phosphoric acid, methyl anyl alcohol, polyacrylamide, polyoxyethylene ether,
It is 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 binder in the graphene/cellulose composite material layer.
Preferably, the mass ratio of the binder and cellulose is (0-10):100, preferably (0-5):100.
Preferably, the binder include butadiene-styrene rubber, Viton, polyvinyl alcohol, hydroxymethyl cellulose salt, polyacrylic acid,
Polyacrylate and its derivative, polyacrylonitrile, acrylic ester-acrylonitrile copolymer, polymethyl methacrylate, dimethyl two
One of acrylic 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 battery includes claim 1-8 described in any item diaphragms or any
The diaphragm that item the method is prepared.
10. lithium ion battery according to claim 9, which is characterized in that the lithium ion battery is button cell, stacking
At least one of formula battery, coiled battery；
Preferably, the outer packing of the lithium ion battery is that flexible packaging or steel shell are packed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710392500.8A CN108933216B (en) | 2017-05-27 | 2017-05-27 | Diaphragm containing graphene/cellulose composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710392500.8A CN108933216B (en) | 2017-05-27 | 2017-05-27 | Diaphragm containing graphene/cellulose composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108933216A true CN108933216A (en) | 2018-12-04 |
| CN108933216B CN108933216B (en) | 2020-10-30 |
Family
ID=64451456
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710392500.8A Active CN108933216B (en) | 2017-05-27 | 2017-05-27 | Diaphragm containing graphene/cellulose composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108933216B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111162231A (en) * | 2019-12-27 | 2020-05-15 | 清华大学 | Multifunctional diaphragm for lithium battery and preparation method and application thereof |
| CN112309609A (en) * | 2020-10-10 | 2021-02-02 | 山东华冠智能卡有限公司 | Water-based graphene conductive paste, preparation method thereof and RFID label |
| CN112952293A (en) * | 2021-01-29 | 2021-06-11 | 枣阳市格芯电子科技有限公司 | Explosion-proof low-internal-resistance lithium ion battery and preparation method thereof |
| WO2023245839A1 (en) * | 2022-06-24 | 2023-12-28 | 宁德时代新能源科技股份有限公司 | Separator, preparation method therefor, and secondary battery and electrical device related thereto |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103427069A (en) * | 2012-05-19 | 2013-12-04 | 湖南省正源储能材料与器件研究所 | Lithium ion battery composite anode material and preparation thereof |
| CN103840125A (en) * | 2012-11-23 | 2014-06-04 | 中国科学院大连化学物理研究所 | Lithium-sulfur battery positive electrode structure and preparation method thereof |
| CN104538573A (en) * | 2014-12-30 | 2015-04-22 | 刘剑洪 | Diaphragm for lithium ion battery and preparation method of diaphragm |
| CN105895870A (en) * | 2016-04-06 | 2016-08-24 | 鸿纳（东莞）新材料科技有限公司 | High-concentration and high-purity graphene slurry and preparation method and application thereof |
| WO2016137147A1 (en) * | 2015-02-26 | 2016-09-01 | 한양대학교 산학협력단 | Separator membrane for secondary battery, method for manufacturing same, and lithium secondary battery comprising same |
| CN106299208A (en) * | 2016-10-12 | 2017-01-04 | 河北金力新能源科技股份有限公司 | A kind of preparation method of high temperature resistant low-resistivity lithium ion battery separator |
-
2017
- 2017-05-27 CN CN201710392500.8A patent/CN108933216B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103427069A (en) * | 2012-05-19 | 2013-12-04 | 湖南省正源储能材料与器件研究所 | Lithium ion battery composite anode material and preparation thereof |
| CN103840125A (en) * | 2012-11-23 | 2014-06-04 | 中国科学院大连化学物理研究所 | Lithium-sulfur battery positive electrode structure and preparation method thereof |
| CN104538573A (en) * | 2014-12-30 | 2015-04-22 | 刘剑洪 | Diaphragm for lithium ion battery and preparation method of diaphragm |
| WO2016137147A1 (en) * | 2015-02-26 | 2016-09-01 | 한양대학교 산학협력단 | Separator membrane for secondary battery, method for manufacturing same, and lithium secondary battery comprising same |
| CN105895870A (en) * | 2016-04-06 | 2016-08-24 | 鸿纳（东莞）新材料科技有限公司 | High-concentration and high-purity graphene slurry and preparation method and application thereof |
| CN106299208A (en) * | 2016-10-12 | 2017-01-04 | 河北金力新能源科技股份有限公司 | A kind of preparation method of high temperature resistant low-resistivity lithium ion battery separator |
Non-Patent Citations (2)
| Title |
|---|
| 江莞，范宇驰，刘霞，王连军: "机械剥离法制备石墨烯及其在石墨烯/陶瓷复合材料制备中的应用", 《中国材料进展》 * |
| 高玉荣，黄培，孙佩佩，吴敏，黄勇: "石墨烯/纤维素复合材料的制备及应用", 《化学进展》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111162231A (en) * | 2019-12-27 | 2020-05-15 | 清华大学 | Multifunctional diaphragm for lithium battery and preparation method and application thereof |
| CN112309609A (en) * | 2020-10-10 | 2021-02-02 | 山东华冠智能卡有限公司 | Water-based graphene conductive paste, preparation method thereof and RFID label |
| CN112309609B (en) * | 2020-10-10 | 2021-06-04 | 山东华冠智能卡有限公司 | Water-based graphene conductive paste, preparation method thereof and RFID label |
| CN112952293A (en) * | 2021-01-29 | 2021-06-11 | 枣阳市格芯电子科技有限公司 | Explosion-proof low-internal-resistance lithium ion battery and preparation method thereof |
| CN112952293B (en) * | 2021-01-29 | 2023-09-05 | 枣阳市格芯电子科技有限公司 | Explosion-proof low-internal-resistance lithium ion battery and preparation method thereof |
| WO2023245839A1 (en) * | 2022-06-24 | 2023-12-28 | 宁德时代新能源科技股份有限公司 | Separator, preparation method therefor, and secondary battery and electrical device related thereto |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108933216B (en) | 2020-10-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105826508B (en) | Piezoelectric ceramics composite diaphragm, preparation method and lithium ion battery | |
| CN106328992B (en) | A kind of preparation method of lithium ion battery and the lithium ion battery | |
| CN107732293B (en) | The preparation method of class sandwich structure solid polymer electrolyte membrane and its application in solid lithium ion battery | |
| CN105470576B (en) | A kind of high pressure lithium battery electric core and preparation method thereof, lithium ion battery | |
| CN108933215A (en) | It is a kind of to include graphene/cellulose composite material battery slurry and its preparation method and application | |
| CN104617328B (en) | A kind of long-life lithium rechargeable battery and its manufacture method | |
| WO2021228193A1 (en) | High-energy-density long-life fast charging lithium ion battery and preparation method therefor | |
| CN108933216A (en) | It is a kind of to include graphene/cellulose composite material diaphragm and preparation method thereof | |
| CN105932209B (en) | Ceramic coating diaphragm for lithium ion battery and preparation method thereof | |
| CN105789556A (en) | Electrode plate and lithium ion battery | |
| CN105185986A (en) | High-capacity cylindrical 18650 lithium-ion battery and preparation method thereof | |
| CN110085792A (en) | A kind of novel lithium battery isolation film and the lithium ion battery containing the isolation film | |
| CN109802094A (en) | A kind of low temperature ferric phosphate lithium cell and preparation method thereof | |
| WO2022000308A1 (en) | Bipolar current collector, electrochemical device, and electronic device | |
| CN113540416A (en) | Solid electrolyte coated graphite composite material, preparation method and application thereof, and lithium ion battery | |
| JP2023518889A (en) | Electrochemical device and electronic device containing the electrochemical device | |
| CN207303231U (en) | A kind of graphene lithium-ion negative pole pole piece | |
| CN110875476A (en) | Negative electrode for lithium secondary battery, method for preparing same, and lithium secondary battery | |
| CN111710900A (en) | Graphene-based lithium iron phosphate anode-silica composite cathode low-temperature high-magnification high-energy-density lithium ion battery | |
| CN111916757A (en) | Multilayer electrode, preparation method of multilayer electrode and lithium ion battery | |
| CN108428564A (en) | A kind of preparation method of lithium-ion capacitor negative plate | |
| CN108933236A (en) | It is a kind of to include graphene/cellulose composite material lithium ion battery and preparation method thereof | |
| CN117691202A (en) | Semi-solid electrode lithium battery and preparation method thereof | |
| CN114883527A (en) | Multilayer negative plate, preparation method thereof and secondary battery | |
| CN113948710A (en) | Positive current collector, positive plate and lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |