CN106469809A - Graphene conductive paper and paper battery and its application - Google Patents
Graphene conductive paper and paper battery and its application Download PDFInfo
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- CN106469809A CN106469809A CN201610206309.5A CN201610206309A CN106469809A CN 106469809 A CN106469809 A CN 106469809A CN 201610206309 A CN201610206309 A CN 201610206309A CN 106469809 A CN106469809 A CN 106469809A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- 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
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- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0563—Liquid materials, e.g. for Li-SOCl2 cells
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The invention provides a kind of graphene conductive paper and paper battery and its application.A kind of graphene conductive paper, mainly by nano-carbon material, paper pulp and auxiliary agent with 10 50%：40 75%：8 18% mass percent is made；Described nano-carbon material includes at least Graphene, and described auxiliary agent is one or more of modified starch, PAMA, polyvinyl alcohol, carboxymethyl cellulose.The present invention is applied to paper battery field to be had the advantages that to improve specific capacity, stable cell performance, improves battery life.
Description
Technical field
The present invention relates to conductive material field, in particular to a kind of graphene conductive paper
And paper battery and its application.
Background technology
The problems such as weight of battery, not bent, capacity, life-span, hampers electronics always and produces
The further lighting of product.Paper battery contributes to mitigating the weight of electronic product, extends product
Life-span, and give battery certain pliability, play and mutually push away with light flexible electronic product
Dynamic effect.
Using ripe paper technology, conductible paper is used as current collector and electrode, provides
A kind of thinking of low cost, lightweight and efficient energy reservess.At present the whole world only the U.S.,
There is certain developmental achievement in several country such as Israel, Finland, Sweden in this area.Paper electricity
Pond is mainly with fibrous paper as carrier, is coated with the ink that nano material is made or prints,
Constitute battery or ultracapacitor.This paper battery can be cut out, bend, environmentally friendly
And cost is not high.Its application is related to RF Reader (RFID), electronic tag, intelligence
Card etc., potential application field is then related to many electronic products such as mobile phone, laptop computer.
The nano-carbon materials such as conduction active-carbon, CNT, Graphene are excellent due to having
Electric conductivity and stable physical and chemical performance, receive more and more attention in paper battery research,
Especially Graphene.Such as CN103966907A, CN102619128B,
The patent applications such as CN102169999B all have studied nano-carbon material in paper battery or paper electrode
In application, these technical schemes are all simply to be blended in nano-carbon material with paper pulp
Make paper electrode together, or be additionally added electrode active material, do not consider nano-sized carbon
The impact to paper battery electric conductivity for the mixed effect of material and paper pulp, leads to the conduction of electrode
Performance improve inconspicuous it is impossible to give full play to the superiority of nano-carbon material.
In view of this, the special proposition present invention.
Content of the invention
The first object of the present invention is to provide a kind of graphene conductive paper, described Graphene
Conductive paper both can be as the positive pole of paper battery it is also possible to negative pole as paper battery, application
In paper battery field, there is raising specific capacity, stable cell performance, raising battery life etc. excellent
Point.
The second object of the present invention is to provide a kind of graphene paper battery, described Graphene
Paper battery has the advantages that battery capacity height, stable performance, life-span length.
The third object of the present invention there are provided the application of graphene conductive paper, and this application is non-
Often extensive, including the power supply for making wearable device or dress ornament, or lead for making
Power supply of electric facial film etc., the present invention is applied to be not intended to limit.
In order to realize above-mentioned first purpose of the present invention, spy employs the following technical solutions：
A kind of graphene conductive paper, mainly by nano-carbon material, paper pulp and auxiliary agent with 10-50%：
40-75%：The mass percent of 8-18% is made；Described nano-carbon material includes at least stone
Black alkene, described auxiliary agent is modified starch, PAMA, polyvinyl alcohol, carboxylic first
One or more of base cellulose.
Compared with prior art, the above-mentioned graphene conductive paper of the present invention mainly chemically forms
On optimize the interpolation type of auxiliary agent and itself and nano-carbon material, the proportioning of paper pulp, thus
Improve conductive combination property.
Specifically, first compared with prior art, the conductive paper of the present invention has and preferably leads
Electrical property, improves the dispersibility of nano-carbon material and crystal grain by adding specific auxiliary agent
Granularity, so that conductive paper has electric conductivity evenly and resistance adjustability, herein
" resistance adjustability " refers to when the auxiliary agent species adding is different or content is different, conductive
The resistance value of paper is different, and this ensures that conductive paper can be used for different fields, for example electricity
Hinder relatively low conductive paper and can be used for electrical heating (high current is produced by low resistance and heats object)
Material Field, the higher conductive paper of resistance can be used for low current transmission material, above-mentioned conductive paper
Resistance within 20-2000 Ω/sq scalable.In addition, the present invention passes through to optimize each raw material
Between proportioning the problems such as avoid electrostatic, improve mechanical strength and the change of conductive paper simultaneously
Learn stability.
Next is also prior, and the present invention plays cementation, anion from modified starch
These specific auxiliary agents of polyacrylamide, polyvinyl alcohol, carboxymethyl cellulose improve graphite
The dispersion effect of alkene, makes this conductive paper both can serve as the negative pole of paper battery it is also possible to be used as
Positive pole；And it has the appearance of the electrode active material of storage opposition bigger than existing electrode
Amount, thus corresponding battery also has bigger capacitance；And the conduction due to the present invention
Paper has more stable charge-discharge performance, the battery that therefore present invention makes than existing electrode
Life-span is longer, and that is, the loss rate of capacitance is slow.
In addition, when above-mentioned conductive paper uses as positive pole paper or negative pole paper, it is corresponding another
Electrode can adopt arbitrarily available electrode material.
The preferred modified starch of auxiliary agent of the present invention and polyvinyl alcohol.
Graphene of the present invention includes graphene nano lamella and Graphene, wraps further
Include biomass graphene nano lamella and biomass Graphene.
Graphene of the present invention can be obtained by different preparation methoies, such as mechanical stripping
Method, epitaxial growth method, chemical vapor infiltration, graphite oxidation reducing process, can also be logical
Cross to biomass resource hydrothermal carbonization method, and the graphite that in prior art prepared by other methods
Alkene.But, which kind of method is all difficult to realize to prepare stricti jurise theory on a large scale
On Graphene, such as can there is some impurity unit in the Graphene that prior art prepares
The graphene-structured of element, other allotropes of carbon or the non-monolayer of the number of plies or even multilamellar
(such as 3 layers, 5 layers, 10 layers, 20 layers etc.), the Graphene that the present invention is utilized also wraps
Include the Graphene on above-mentioned non-critical theory of meaning.
Graphene nano lamella can adopt Jinan holy well company technique, based on agriculture and forestry organic waste material
Want raw material, obtained by steps such as hydrolysis, catalytic treatment, heat treatments and there is good electric conductivity
The multiporous biological matter graphene complex of matter, it is mainly characterized by the contained Graphene number of plies and is
Between 1～10 layer, non-carbon nonoxygen element content is 0.5wt%～6wt%.
Above-mentioned conductive paper can also improve further, to improve its effect：
Preferably, described nano-carbon material also includes at least in carbon fiber and CNT
Kind.
After increasing carbon fiber or CNT, equally can form conductive network and lead to increase
The electric conductivity of electric paper, can also reduce the consumption of Graphene, to reduce cost of material.
Preferably, in described nano-carbon material the weight of Graphene than for 20%-40%.
The content of Graphene is unsuitable too low, and otherwise capacitance is undesirable；Also unsuitable too high, no
Dispersion difficulty then can be increased, improve cost of material.
Preferably, the mass percent of described nano-carbon material, described paper pulp and described auxiliary agent
It is respectively：10-40%, 50-75%, 10-15%.
The conductive paper negative pole as battery preferably of this composition.
Preferably, the mass percent of described nano-carbon material, described paper pulp and described auxiliary agent
It is respectively：30-50%, 40-56%, 10-14%.
The conductive paper positive pole as battery preferably of this composition.
Preferably, described paper pulp is nanofiber paper pulp.
The fibre pulp of Nano grade with the compatibility of Graphene more preferably, and divides to Graphene
Scattered property is more preferable.
The all conductive papers of invention discussed above can adopt simple preparation method：
All raw materials are mixed recycled paper, described papermaking operation refers mainly to the process mixing and being dried.
It is of course also possible to using other feasible manufacture methods.
In order to realize above-mentioned second purpose of the present invention, spy employs the following technical solutions：
A kind of graphene paper battery, in the positive pole paper of described graphene paper battery or negative pole paper
One main graphene conductive paper by mentioned earlier is made.
Above-mentioned graphene paper battery relate to two types：A kind of is conductive paper with the present invention
As positive pole, another kind is using the conductive paper of the present invention as negative pole；As described above, this
Two kinds of batteries all have the advantages that battery capacity height, stable performance, life-span length.
Wherein, when described positive pole paper is mainly made up of described graphene conductive paper, described negative
Pole paper is less than the tinsel of positive pole paper or the metal coating being coated on matrix for potential；Described
Tinsel or described metal coating are preferably lithium metal or magnesium.Certainly active material not only limits
In both, as long as being capable of reversible charging/discharging function.
When described positive and negative electrode paper is mainly made up of described graphene conductive paper, described positive pole
Paper at least also contains positive electrode active materials；Certainly active material is not limited only to that this is several, as long as
It is capable of reversible charging/discharging function.Wherein, described positive electrode active materials are preferably
One of LiMn2O4, cobalt acid lithium, LiFePO4, LiFePO 4, ternary nickel cobalt manganese or
Multiple, these materials are larger with the potential difference of conductive paper of the present invention, can improve battery capacity.
Generally, the structure of described graphene paper battery is：By described positive pole paper, diaphragm paper and
Described negative pole paper is overrided to form successively, and described positive pole paper, described diaphragm paper and described negative
Pole paper impregnated in electrolyte and encapsulates.
Wherein, diaphragm paper can adopt any materials, as long as playing the effect of isolation positive pole and negative pole
?.Electrolyte mainly the material according to positive pole and negative pole selecting it is ensured that discharge and recharge
The chemical reaction occurring in journey is reversible.
When making the finished product of above-mentioned paper battery, for positive pole paper, diaphragm paper and negative pole paper all
It is adsorbed with enough electrolyte, avoid electrolyte excessive again, paper battery can be encapsulated,
And so that lug is exposed outside, then inject electrolyte to encapsulation is internal.The present invention is to this encapsulation simultaneously
It is not restricted.
In addition, when described negative pole paper is made up of described graphene conductive paper, described positive pole paper
Surface be additionally provided with carbon current collector layer.
Spraying carbon current collector layer can improve the electric conductivity of positive pole, thus improving the discharge and recharge of battery
Speed.
Compared with prior art, beneficial effects of the present invention are：
(1) provide a kind of electric conductivity evenly, resistance is adjustable, no electrostatic problem, machinery
Intensity and chemical stability is higher, conductive paper that is can improving battery capacity and service life；
(2) a kind of capacity height, stable performance, the paper battery of life-span length are provided；
(3) widened the application of conductive paper and paper battery, be conductive paper and paper battery
Industrial applications open new way；
Specific embodiment
Below in conjunction with embodiment, embodiment of the present invention is described in detail, but this
Skilled person will be understood that, the following example is merely to illustrate the present invention, and should not regard
For limiting the scope of the present invention.Unreceipted actual conditions person in embodiment, according to normal condition
Or the condition of manufacturer's suggestion is carried out.Agents useful for same or the unreceipted production firm person of instrument, all
For the conventional products that can be obtained by commercially available purchase.
Embodiment 1
A kind of paper battery：
With nano-cellulose as raw material, prepare fibre pulp, then obtained by paper technology fine
Dimension paper is as diaphragm paper.
By biomass Graphene, CNT and LiFePO 4, according to 2：1：7 ratio
Example dispersion in ethanol, and add 0.5% in amount of substance mixed above macromolecule dispersing agent-
Polyvinylpyrrolidone, makes solid content in solution reach 10% and no sedimentation phenomenon generation, with
Afterwards through being sufficiently stirred for and being dried, LiFePO 4 granule can uniformly be coated by material with carbon element.Will
Dried composite positive pole and fibre pulp, polyvinyl alcohol are according to 4：5：1 is mixed
Merge papermaking, obtain Graphene/active material anode composite paper.
By biomass Graphene, CNT, fibre pulp, polyvinyl alcohol according to 1：3：
5：1 ratio mixing papermaking, obtain material with carbon element composite negative pole paper.
According to Graphene/active material anode composite paper, diaphragm paper, material with carbon element composite negative pole paper
Order stack gradually or be repeatedly laminated successively, the positive pole scraps of paper and the negative pole scraps of paper be respectively connected to
Each it is packaged after collector.After reserved opening evacuation when to encapsulation, then will fit
Amount lithium hexafluoro phosphate injection, finally closes reserved opening.Packaged paper battery is carried out hole milling,
Collector accesses circuit and forms rechargeable type scraps of paper lithium battery.
Embodiment 2
A kind of paper battery：
With nano-cellulose as raw material, prepare fibre pulp, then obtained by paper technology fine
Dimension paper is as diaphragm paper.
By biomass Graphene, CNT and LiFePO 4, according to 2：1：7 ratio
Example dispersion in ethanol, and add 0.5% in amount of substance mixed above macromolecule dispersing agent-
Polyvinylpyrrolidone, makes solid content in solution reach 10% and no sedimentation phenomenon generation, with
Afterwards through being sufficiently stirred for and being dried, LiFePO 4 granule can uniformly be coated by material with carbon element.Will
Dried composite positive pole and fibre pulp, polyvinyl alcohol are according to 4：5：1 is mixed
Merge papermaking, obtain Graphene/active material anode composite paper.
By biomass Graphene, CNT, fibre pulp, polyvinyl alcohol according to 2：8：
75：15 ratio mixing papermaking, obtain material with carbon element composite negative pole paper.
According to Graphene/active material anode composite paper, diaphragm paper, material with carbon element composite negative pole paper
Order stack gradually or be repeatedly laminated successively, the positive pole scraps of paper and the negative pole scraps of paper be respectively connected to
Each it is packaged after collector.After reserved opening evacuation when to encapsulation, then will fit
Amount lithium hexafluoro phosphate injection, finally closes reserved opening.Packaged paper battery is carried out hole milling,
Collector accesses circuit and forms rechargeable type scraps of paper lithium battery.
Embodiment 3
A kind of paper battery：
With nano-cellulose as raw material, prepare fibre pulp, then obtained by paper technology fine
Dimension paper is as diaphragm paper.
By biomass Graphene, CNT and LiFePO 4, according to 2：1：7 ratio
Example dispersion in ethanol, and add 0.5% in amount of substance mixed above macromolecule dispersing agent-
Polyvinylpyrrolidone, makes solid content in solution reach 10% and no sedimentation phenomenon generation, with
Afterwards through being sufficiently stirred for and being dried, LiFePO 4 granule can uniformly be coated by material with carbon element.Will
Dried composite positive pole and fibre pulp, polyvinyl alcohol are according to 4：5：1 is mixed
Merge papermaking, obtain Graphene/active material anode composite paper.
By biomass Graphene, CNT, fibre pulp, polyvinyl alcohol according to 2：3：
4：1 ratio mixing papermaking, obtain material with carbon element composite negative pole paper.
According to Graphene/active material anode composite paper, diaphragm paper, material with carbon element composite negative pole paper
Order stack gradually or be repeatedly laminated successively, the positive pole scraps of paper and the negative pole scraps of paper be respectively connected to
Each it is packaged after collector.After reserved opening evacuation when to encapsulation, then will fit
Amount lithium hexafluoro phosphate injection, finally closes reserved opening.Packaged paper battery is carried out hole milling,
Collector accesses circuit and forms rechargeable type scraps of paper lithium battery.
Embodiment 4
A kind of paper battery：
With nano-cellulose as raw material, prepare fibre pulp, then obtained by paper technology fine
Dimension paper is as diaphragm paper.
By biomass Graphene, carbon fiber and LiFePO 4, according to 2：1：7 ratio
Dispersion in ethanol, and adds 0.5% in the macromolecule dispersing agent-poly- of amount of substance mixed above
Vinylpyrrolidone, makes solid content in solution reach 10% and no sedimentation phenomenon generation, subsequently
Through being sufficiently stirred for and being dried, LiFePO 4 granule can uniformly be coated by material with carbon element.To do
Dry good composite positive pole and fibre pulp, polyvinyl alcohol are according to 4：5：1 is mixed
And papermaking, obtain Graphene/active material anode composite paper.
By biomass Graphene, carbon fiber, fibre pulp, polyvinyl alcohol according to 1：3：5：
1 ratio mixing papermaking, obtain material with carbon element composite negative pole paper.
According to Graphene/active material anode composite paper, diaphragm paper, material with carbon element composite negative pole paper
Order stack gradually or be repeatedly laminated successively, the positive pole scraps of paper and the negative pole scraps of paper be respectively connected to
Each it is packaged after collector.After reserved opening evacuation when to encapsulation, then will fit
Amount lithium hexafluoro phosphate injection, finally closes reserved opening.Packaged paper battery is carried out hole milling,
Collector accesses circuit and forms rechargeable type scraps of paper lithium battery.
Embodiment 5
A kind of paper battery：
With nano-cellulose as raw material, prepare fibre pulp, then obtained by paper technology fine
Dimension paper is as barrier film.
By biomass Graphene, carbon fiber and nickel-cobalt-manganese ternary material, according to 3：1：6 ratio
Example dispersion in ethanol, and add 0.5% in amount of substance mixed above macromolecule dispersing agent-
Polyvinylpyrrolidone, makes solid content in solution reach 10% and no sedimentation phenomenon generation, with
Afterwards through being sufficiently stirred for and being dried, ternary material granule can uniformly be coated by material with carbon element.To do
Dry good composite positive pole and fibre pulp, polyvinyl alcohol are according to 3：6：1 is mixed
And papermaking, obtain Graphene/active material anode composite paper.
With biomass Graphene as raw material, it is soluble in water to be equipped with macromolecule dispersing agent, obtains solid
The slurry of content 12%.This slurry is sprayed at Graphene/active material anode composite scraps of paper table
Face is simultaneously dried, and obtains surface carbon current collector layer.
By biomass Graphene, carbon fiber, fibre pulp, polyvinyl alcohol according to 1：3：5：
1 ratio mixing papermaking, obtain material with carbon element composite negative pole paper.
According to Graphene/active material anode composite paper, diaphragm paper, material with carbon element composite negative pole paper
Order stack gradually or be repeatedly laminated successively, positive pole scraps of paper current collector layer and the negative pole scraps of paper are respectively
It is packaged after accessing to respective collector.After reserved opening evacuation when to encapsulation,
Again appropriate lithium hexafluoro phosphate is injected, finally close reserved opening.Packaged paper battery is entered
Row hole milling, collector accesses circuit and forms rechargeable type scraps of paper lithium battery.
Embodiment 6
A kind of paper battery：
With nano-cellulose for raw material papermaking, obtain nano-cellulose paper as barrier film, should be every
The pliability of film and intensity are all very high, and have higher porosity, suitable electrolyte
Absorption.
By Graphene and carbon fiber, nano-cellulose paper pulp, polyvinyl alcohol according to 1：4：4：
1 ratio mixing carries out papermaking, obtains porous carbon materials conduction paper structure, as positive pole paper
Piece.
According to porous carbon materials conductive paper, diaphragm paper, the order of lithium piece stacks gradually or successively
Repeatedly it is laminated, positive pole scraps of paper current collector layer and negative pole lithium piece are respectively connected to laggard to respective collector
Row encapsulation.After reserved opening evacuation when to encapsulation, more appropriate lithium hexafluoro phosphate is noted
Enter, finally close reserved opening.Packaged paper battery is carried out hole milling, collector accesses electricity
Road forms disposable scraps of paper lithium battery.
Embodiment 7
A kind of paper battery：
With nano-cellulose for raw material papermaking, obtain nano-cellulose paper as barrier film, should be every
The pliability of film and intensity are all very high, and have higher porosity, suitable electrolyte
Absorption.
By Graphene and carbon fiber, nano-cellulose paper pulp, polyvinyl alcohol according to 2：3：4：
1 ratio mixing carries out papermaking, obtains porous carbon materials conduction paper structure.Again by this conduction
Paper is immersed in silver chloride solution and with post-drying, as positive pole.
According to chloride containing silver porous carbon materials conductive paper, diaphragm paper, the order layer successively of magnesium sheet
Fold or be repeatedly laminated successively, positive pole scraps of paper current collector layer and negative pole magnesium sheet are respectively connected to collect to respective
It is packaged after fluid.After reserved opening evacuation when to encapsulation, then by appropriate chlorination
Magnesium solution injects, and finally closes reserved opening.Packaged paper battery is carried out hole milling, afflux
Body accesses circuit and forms disposable scraps of paper magnesium cell.
The magnesium sheet of this embodiment can be substituted with magnesium alloy plate, the performance shadow to battery after replacement
Ring less.
Embodiment 8
A kind of paper battery：
With nano-cellulose as raw material, prepare fibre pulp, then obtained by paper technology fine
Dimension paper is as diaphragm paper.
By biomass Graphene, CNT and cobalt acid lithium, according to 2：1：7 ratio is divided
Dissipate in ethanol and add a certain amount of macromolecule dispersing agent, so that solid content in solution is reached
10% and no sedimentation phenomenon occur, then pass through and be sufficiently stirred for and be dried, material with carbon element can be by phosphorus
Ferrous silicate lithium granule uniformly coats.By dried composite positive pole and fibre pulp, change
Property starch is according to 4：5：1 carries out mixing papermaking, obtains Graphene/active material and is just combined
Pole paper.
By biomass Graphene, CNT, fibre pulp, modified starch according to 1：3：
5：1 ratio mixing papermaking, obtain material with carbon element composite negative pole paper.
According to Graphene/active material anode composite paper, diaphragm paper, material with carbon element composite negative pole paper
Order stack gradually or be repeatedly laminated successively, the positive pole scraps of paper and the negative pole scraps of paper be respectively connected to
Each it is packaged after collector.After reserved opening evacuation when to encapsulation, then will fit
Amount lithium hexafluoro phosphate injection, finally closes reserved opening.Packaged paper battery is carried out hole milling,
Collector accesses circuit and forms rechargeable type scraps of paper lithium battery.
Embodiment 9
A kind of paper battery：
With nano-cellulose as raw material, prepare fibre pulp, then obtained by paper technology fine
Dimension paper is as diaphragm paper.
By biomass Graphene, CNT and LiMn2O4, according to 2：1：7 ratio is divided
Dissipate in ethanol and add a certain amount of macromolecule dispersing agent, so that solid content in solution is reached
10% and no sedimentation phenomenon occur, then pass through and be sufficiently stirred for and be dried, material with carbon element can be by phosphorus
Ferrous silicate lithium granule uniformly coats.By dried composite positive pole and fibre pulp, the moon
Cationic polyacrylamide is according to 4：5：1 carries out mixing papermaking, obtains Graphene/activity material
Material anode composite paper.
Biomass Graphene, CNT, fibre pulp, PAMA are pressed
According to 1：3：5：1 ratio mixing papermaking, obtain material with carbon element composite negative pole paper.
According to Graphene/active material anode composite paper, diaphragm paper, material with carbon element composite negative pole paper
Order stack gradually or be repeatedly laminated successively, the positive pole scraps of paper and the negative pole scraps of paper be respectively connected to
Each it is packaged after collector.After reserved opening evacuation when to encapsulation, then will fit
Amount lithium hexafluoro phosphate injection, finally closes reserved opening.Packaged paper battery is carried out hole milling,
Collector accesses circuit and forms rechargeable type scraps of paper lithium battery.
Embodiment 10
A kind of paper battery：
With nano-cellulose as raw material, prepare fibre pulp, then obtained by paper technology fine
Dimension paper is as diaphragm paper.
By biomass Graphene, CNT and LiFePO4, according to 2：1：7 ratio
Dispersion in ethanol and adds a certain amount of macromolecule dispersing agent, so that solid content in solution is reached
10% and no sedimentation phenomenon occur, then pass through and be sufficiently stirred for and be dried, material with carbon element can be by phosphorus
Ferrous silicate lithium granule uniformly coats.By dried composite positive pole and fibre pulp, carboxylic
Methylcellulose is according to 4：5：1 carries out mixing papermaking, obtains Graphene/active material multiple
Close positive pole paper.
By biomass Graphene, CNT, fibre pulp, carboxymethyl cellulose according to 1：
3：5：1 ratio mixing papermaking, obtain material with carbon element composite negative pole paper.
According to Graphene/active material anode composite paper, diaphragm paper, material with carbon element composite negative pole paper
Order stack gradually or be repeatedly laminated successively, the positive pole scraps of paper and the negative pole scraps of paper be respectively connected to
Each it is packaged after collector.After reserved opening evacuation when to encapsulation, then will fit
Amount lithium hexafluoro phosphate injection, finally closes reserved opening.Packaged paper battery is carried out hole milling,
Collector accesses circuit and forms rechargeable type scraps of paper lithium battery.
Embodiment 11
A kind of fever type conductive paper：
By biomass Graphene, CNT, fibre pulp, polyvinyl alcohol according to 1：3：
5：1 ratio mixing papermaking, obtain material with carbon element composite conductive paper.Starch (silver paste) using copper
Go out electrode and circuit in conductive paper surface printing.Then heating paper makes and finishes.Finally, use
Insulating barrier (material such as PET) carries out overall package to heating paper.
The heating paper that the present embodiment obtains is light, pliability good it is adaptable to little running voltage work
Make, the suitable human body of operating temperature bears.Clothing can be embedded, in personal care's wearable items,
It is powered using 3.7V voltage, by adjusting voltage output, temperature control can be made in 30-60
Degree Celsius.
Experiment
Investigate the performance of the battery that above example provides, and compare with prior art, knot
Fruit such as table 1.
The performance of table 1 paper battery
| Specific capacity | 500 circle circulation behind efficiencies | |
| Embodiment 1 | 4mAh/cm2 | 87% |
| Embodiment 2 | 3.7mAh/cm2 | 89% |
| Embodiment 3 | 4.1mAh/cm2 | 85% |
| Embodiment 4 | 4mAh/cm2 | 85% |
| Embodiment 5 | 5.5mAh/cm2 | 80% |
| Embodiment 6 | 38mAh/cm2 | Disposable battery can not fill |
| Embodiment 7 | 42mAh/cm2 | Disposable battery can not fill |
| Embodiment 8 | 3.2mAh/cm2 | 90% |
| Embodiment 9 | 2.5mAh/cm2 | 89% |
| Embodiment 10 | 3.8mAh/cm2 | 82% |
| Contrast 1 | 2.5-5mAh/cm2 | Disposable battery can not fill |
Contrasting 1 is：Powerpaper company of Israel paper battery patent HK20010101229,
Using electrode material be respectively zinc and manganese dioxide, electrolyte be zinc chloride.
The method of testing of specific capacity：Using conventional blue electricity battery test system test charge and discharge electric capacity
Amount.
The method of testing of cycle efficieny：Using conventional blue electricity battery test system.
Although illustrate and describing the present invention with specific embodiment, but it will be appreciated that
Can make without departing from the spirit and scope of the present invention many other changes and
Modification.It is, therefore, intended that including in the following claims belonging in the scope of the invention
All such changes and modifications.
Claims (10)
1. a kind of graphene conductive paper is it is characterised in that be mainly made up with the mass percent of 10-50%, 40-75%, 8-18% of material with carbon element, paper pulp and auxiliary agent；Described material with carbon element includes at least Graphene, and described auxiliary agent is one or more of modified starch, PAMA, polyvinyl alcohol, carboxymethyl cellulose.
2. graphene conductive paper according to claim 1 is it is characterised in that described material with carbon element also includes at least one of carbon fiber and CNT；Described paper pulp is preferably nanofiber paper pulp.
3. graphene conductive paper according to claim 1 and 2 it is characterised in that in described material with carbon element Graphene content be 20wt%-40wt%.
4. graphene conductive paper according to claim 1 is it is characterised in that the mass percent of described material with carbon element, described paper pulp and described auxiliary agent is respectively：10-40%、50-75%、10-15%.
5. graphene conductive paper according to claim 1 is it is characterised in that the mass percent of described material with carbon element, described paper pulp and described auxiliary agent is respectively：30-50%、40-56%、10-14%.
6. a kind of graphene paper battery is it is characterised in that the main graphene conductive paper described in any one of claim 1-5 of one of the positive pole paper of described graphene paper battery or negative pole paper is made.
7. it is characterised in that described positive pole paper is mainly made up of described graphene conductive paper, described negative pole paper is less than the tinsel of positive pole paper or the metal coating being coated on matrix for potential to graphene paper battery according to claim 6；Described tinsel or described metal coating are preferably lithium metal or magnesium.
8. graphene paper battery according to claim 6 is it is characterised in that described positive and negative electrode paper is mainly made up of described graphene conductive paper, and described positive pole paper at least contains positive electrode active materials；Described positive electrode active materials are preferably one or more of LiMn2O4, cobalt acid lithium, LiFePO4, LiFePO 4, ternary nickel cobalt manganese.
9. the graphene paper battery according to any one of claim 6-8, it is characterized in that, described graphene paper battery is overrided to form successively by described positive pole paper, diaphragm paper and described negative pole paper, and described positive pole paper, described diaphragm paper and described negative pole paper impregnated in electrolyte and encapsulates.
10. the application of the graphene conductive paper described in any one of claim 1-5 is it is characterised in that described graphene conductive paper is used for making the power supply of wearable device or dress ornament, or for making the power supply of conducting mask.
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| PCT/CN2017/079335 WO2017167312A1 (en) | 2016-04-01 | 2017-04-01 | Composite material for paper electrode, paper electrode, conductive graphene sheet, paper battery, and application thereof |
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| CN108172760A (en) * | 2017-12-25 | 2018-06-15 | 北京乐华锂能科技有限公司 | A kind of paper combination electrode and preparation method thereof |
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| CN108260887A (en) * | 2017-12-30 | 2018-07-10 | 东莞市明骏智能科技有限公司 | A kind of carbon nanotube electric heating assembly, electric heating insole and Electrothermal shoes |
| CN111009649A (en) * | 2019-12-19 | 2020-04-14 | 内蒙古瀚璞科技发展有限公司 | Silicon negative electrode material of all-solid-state lithium ion battery and preparation method thereof |
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