WO2017167312A1 - Composite material for paper electrode, paper electrode, conductive graphene sheet, paper battery, and application thereof - Google Patents

Composite material for paper electrode, paper electrode, conductive graphene sheet, paper battery, and application thereof Download PDF

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Publication number
WO2017167312A1
WO2017167312A1 PCT/CN2017/079335 CN2017079335W WO2017167312A1 WO 2017167312 A1 WO2017167312 A1 WO 2017167312A1 CN 2017079335 W CN2017079335 W CN 2017079335W WO 2017167312 A1 WO2017167312 A1 WO 2017167312A1
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Prior art keywords
paper
graphene
positive electrode
battery
electrode
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PCT/CN2017/079335
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French (fr)
Chinese (zh)
Inventor
张金柱
刘顶
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济南圣泉集团股份有限公司
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Priority claimed from CN201610203943.3A external-priority patent/CN106469808B/en
Priority claimed from CN201610206309.5A external-priority patent/CN106469809A/en
Application filed by 济南圣泉集团股份有限公司 filed Critical 济南圣泉集团股份有限公司
Publication of WO2017167312A1 publication Critical patent/WO2017167312A1/en

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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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • 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
    • 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
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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

Definitions

  • the present invention relates to the field of conductive materials, and in particular to composite materials for paper electrodes, paper electrodes, paper batteries, graphite conductive paper, paper batteries, and applications thereof.
  • Paper batteries help to reduce the weight of electronic products, extend the life of the product, and give the battery a certain degree of flexibility, which promotes the interaction with flexible and lightweight electronic products.
  • the paper battery is mainly coated with fiber paper as a carrier and coated or printed with ink made of nano material to form a battery or a super capacitor. This paper battery can be cut, bent, environmentally friendly and inexpensive. Its application fields include radio frequency identification (RFID), electronic tags, smart cards, etc., and potential applications include mobile phones, laptops and many other electronic products.
  • RFID radio frequency identification
  • Nano-carbon materials such as conductive activated carbon, carbon nanotubes, and graphene have attracted more and more attention in paper battery research due to their excellent electrical conductivity and stable physical and chemical properties, especially graphene.
  • CN103966907A, CN102619128B, CN102169999B and other patent applications have studied the application of nano-carbon materials in paper batteries or paper electrodes. These technical solutions simply mix nano-carbon materials with pulp to make paper electrodes, or add them.
  • the electrode active material does not consider the influence of the mixing effect of the nano carbon material and the pulp on the electrical conductivity of the paper battery, and the conductivity of the electrode is not improved significantly, and the superiority of the nano carbon material cannot be fully utilized.
  • Another object of the present invention is to provide a graphene conductive paper, which can be used as a positive electrode of a paper battery or as a negative electrode of a paper battery, and has a specific capacity and a stable battery in the field of paper batteries. Performance, improved battery life and other advantages.
  • a further object of the present invention is to provide an application of graphene conductive paper, which is very widely used, including a power source for manufacturing a wearable device or clothing, or a power source for producing a conductive mask, etc., and the present invention is not applied thereto. limit.
  • a composite material for a paper electrode mainly composed of a carbon material, a pulp and an auxiliary agent in a mass ratio of 5-10:34-57:6-9; the carbon material containing at least graphene, the auxiliary
  • the agent is one or more selected from the group consisting of modified starch, anionic polyacrylamide, polyvinyl alcohol, and carboxymethyl cellulose.
  • the composite material of the invention mainly optimizes the addition type of the auxiliary agent and its ratio with the nano carbon material and the pulp, thereby improving the coating effect on the paper electrode.
  • the composite material of the invention has better encapsulation, and on the one hand, can effectively limit the volume expansion of the electrode active material (especially the positive electrode active material), thereby improving the service life of the electrode.
  • the conductive path is fixed; on the other hand, due to the existence of the two-dimensional material-graphene, the electrode active material is in surface contact with the composite material, thereby greatly improving the conductivity of the active material.
  • the present invention adds a specific type of specific ratio of auxiliary agents to reduce the adverse effects of the coating on the paper electrode to a lower level or even a zero level.
  • the present invention avoids problems such as static electricity by optimizing the ratio between the respective raw materials, and can improve mechanical strength and chemical stability when coating the paper electrode.
  • the composite material of the present invention can stabilize the charge and discharge performance of the paper electrode, the paper electrode produced by the present invention has a longer life, and the battery capacity of the produced paper battery is slow.
  • the above composite material is mainly used for the positive electrode, and the corresponding active material needs to be added when coating the electrode, and there are various methods for coating, and all the raw materials of the composite material and the active material can be mixed and made by paper, or other feasible methods can be adopted. .
  • the present invention is not limited to other coating methods and other uses.
  • the content of graphene in the nanocarbon material is preferably from 65 wt% to 75 wt%.
  • the content of graphene should not be too low, otherwise the capacity is not ideal; it should not be too high, otherwise it will increase the difficulty of dispersion and increase the cost of raw materials.
  • a graphene conductive paper mainly made of nano carbon material, pulp and auxiliary agent in a mass percentage of 10-50%: 40-75%: 8-18%; the nano carbon material contains at least graphene,
  • the auxiliary agent is one or more selected from the group consisting of modified starch, anionic polyacrylamide, polyvinyl alcohol, and carboxymethyl cellulose.
  • the above graphene conductive paper of the present invention mainly optimizes the chemical composition from the auxiliary agent.
  • the type of addition and its ratio to nano-carbon materials and pulp improve the electrical conductivity.
  • the conductive paper of the present invention has better electrical conductivity than the prior art, and the dispersibility of the nano carbon material and the grain size of the crystal grains are improved by adding a specific auxiliary agent, thereby making the conductive paper more uniform.
  • Conductivity and resistance adjustability means that when the kinds of additives added are different or the content is different, the resistance values of the conductive paper are different, which can ensure that the conductive paper can be used in different fields.
  • conductive paper with lower resistance can be used for electric heating (heating objects with high electric resistance by low resistance).
  • the conductive paper with higher resistance can be used for low current transmission materials.
  • the resistance of the above conductive paper can be within 20-2000 ⁇ /sq. Adjustment.
  • the present invention avoids problems such as static electricity by optimizing the ratio between the respective raw materials, and at the same time improves the mechanical strength and chemical stability of the conductive paper.
  • the present invention selects modified starch for bonding, and specific additives such as anionic polyacrylamide, polyvinyl alcohol and carboxymethyl cellulose improve the dispersion effect of graphene, so that the conductive paper can be Used as a negative electrode of a paper battery, can also be used as a positive electrode; and it has a larger capacity for storing opposite electrode active materials than existing electrodes, and thus the corresponding battery also has a larger capacitance; and due to the conductive of the present invention Paper has more stable charge and discharge performance than existing electrodes, so the battery produced by the present invention has a longer life, that is, the loss rate of the electric capacity is slow.
  • specific additives such as anionic polyacrylamide, polyvinyl alcohol and carboxymethyl cellulose improve the dispersion effect of graphene, so that the conductive paper can be Used as a negative electrode of a paper battery, can also be used as a positive electrode; and it has a larger capacity for storing opposite electrode active materials than existing electrodes, and thus the corresponding battery also has a
  • the other electrode corresponding thereto may be any available electrode material.
  • the weight ratio of graphene in the nanocarbon material is 20% to 40%.
  • the content of graphene should not be too low, otherwise the capacity is not ideal; it should not be too high, otherwise it will increase the difficulty of dispersion and increase the cost of raw materials.
  • the mass percentages of the nano carbon material, the pulp and the auxiliary agent are respectively 10-40%, 50-75%, 10-15%.
  • the conductive paper of this composition is more suitably used as a negative electrode of a battery.
  • the mass percentages of the nano carbon material, the pulp and the auxiliary agent are respectively 30-50%, 40-56%, 10-14%.
  • the conductive paper of this composition is more suitably used as the positive electrode of the battery.
  • All of the conductive papers of the present invention described above can be prepared by a simple preparation method: mixing all the raw materials and making paper, and the papermaking process mainly refers to a mixing and drying process. Of course, other feasible production methods can also be used.
  • the adjuvant of the present invention is preferably a modified starch and a polyvinyl alcohol.
  • the graphene of the present invention comprises a graphene nanosheet layer and graphene, and further comprises a biomass graphene nanosheet. Layer and biomass graphene.
  • the graphene of the present invention can be obtained by different preparation methods, such as mechanical stripping method, epitaxial growth method, chemical vapor deposition method, graphite redox method, hydrothermal carbonization method for biomass resources, and prior art.
  • Graphene prepared by other methods it is difficult to achieve large-scale preparation of graphene in a strictly theoretical manner by any method. For example, some impurity elements, other allotropes or layers of carbon elements may be present in the graphene prepared by the prior art.
  • Non-monolayer or even multi-layer graphene structures for example, 3 layers, 5 layers, 10 layers, 20 layers, etc.
  • the graphene utilized in the present invention also includes the above-mentioned non-strict theoretical graphene.
  • the graphene nanosheet layer can adopt the process of Jinan Shengquan Company, and the porous biomass graphene composite with excellent conductive properties is obtained by the steps of hydrolysis, catalytic treatment and heat treatment with the agricultural and forestry waste as the main raw material, and its main feature is contained.
  • the number of graphene layers is between 1 and 10 layers, and the content of non-carbon non-oxygen elements is from 0.5% by weight to 6% by weight.
  • the nanocarbon material further comprises at least one of carbon fibers and carbon nanotubes.
  • a conductive network can also be formed to increase the electrical conductivity of the composite material and the conductive paper, and the amount of graphene can be reduced to reduce the raw material cost.
  • the pulp is nanofiber pulp.
  • Nano-grade fiber pulp has better compatibility with graphene and better dispersibility for graphene.
  • the electrical conductivity is more stable and the service life is prolonged.
  • the paper electrode can be prepared by a simple preparation method in which all the raw materials are mixed and then subjected to papermaking, and the papermaking process mainly refers to a process of mixing and drying. Of course, other feasible production methods can also be used.
  • a dispersing agent such as a polymer dispersing agent such as polyacrylamide may be appropriately added.
  • the cathode active material is one or more selected from the group consisting of lithium manganate, lithium cobaltate, lithium iron phosphate, lithium iron phosphate, and ternary nickel cobalt manganese.
  • the mass percentage of the carbon material, the pulp, the auxiliary agent and the positive active material are: 5-10%, 34-57%, 6-9%, 30-50%, respectively.
  • a paper battery comprising a positive paper mainly composed of the paper electrodes described above.
  • the negative electrode paper used in the paper battery of the present invention is not particularly limited, and may be an effective battery if it is combined with the above positive electrode paper.
  • the following negative paper is used: the negative paper is mainly made of the carbon material, the pulp and the auxiliary agent in a mass percentage of 10-50%: 40-75%: 8-18%, and the negative paper is further The further ratio is 10-40%: 50-75%: 10-15%.
  • a graphene paper battery one of a positive or negative paper of the graphene paper battery is mainly made of the graphene conductive paper described above.
  • the above graphene paper batteries are of two types: one is a conductive paper of the present invention as a positive electrode, and the other is a conductive paper of the present invention as a negative electrode; as described above, both of the batteries have a high battery capacity.
  • both of the batteries have a high battery capacity. The advantages of stable performance and long life.
  • the negative electrode paper is a metal foil having a lower potential than the positive electrode paper or a metal coating applied to the substrate; the metal foil or the metal foil
  • the metal coating is preferably metallic lithium or magnesium.
  • the active material is not limited to these two types as long as a reversible charge and discharge function can be achieved.
  • the positive electrode paper further contains at least a positive electrode active material; of course, the active material is not limited to these types as long as a reversible charge and discharge function can be achieved.
  • the positive electrode active material is preferably one or more of lithium manganate, lithium cobaltate, lithium iron phosphate, lithium iron phosphate, and ternary nickel cobalt manganese, and the potential difference between these materials and the conductive paper of the present invention is Large, can increase battery capacity.
  • the above paper battery or the above graphene paper battery is further provided with a separator paper and an electrolyte, that is, the paper battery or the graphene paper battery is sequentially laminated from the positive paper, the separator paper and the negative paper. And the positive electrode paper, the separator paper, and the negative electrode paper are immersed in the electrolytic solution and encapsulated.
  • the separator paper can be any material as long as it functions to isolate the positive electrode and the negative electrode.
  • the electrolyte is mainly selected according to the materials of the positive electrode and the negative electrode, and it is necessary to ensure that the chemical reaction occurring during charging and discharging is reversible.
  • the paper battery in order to adsorb sufficient electrolyte for the positive paper, the separator paper and the negative paper, and avoid excessive electrolyte, the paper battery can be packaged, and the tabs are exposed and then exposed to the package. Inject the electrolyte.
  • the present invention is not limited to this package.
  • the electrolyte is one or more of lithium hexafluorophosphate, lithium perchlorate, and lithium tetrafluoroborate.
  • a carbon current collector layer may be further provided on the positive electrode paper used in the present invention.
  • the surface of the positive paper is further provided with a carbon current collecting layer.
  • the carbon current collecting layer can improve the conductivity of the electrode, thereby increasing the charge and discharge rate of the battery, and preferably forming a carbon current collecting layer on the surface of the positive electrode by spraying.
  • the beneficial effects of the present invention include at least:
  • a paper battery 1
  • the fiber pulp is prepared by using nanocellulose as a raw material, and the fiber paper is obtained by a papermaking process and used as a separator paper.
  • the biomass graphene, the carbon nanotubes and the lithium iron phosphate are dispersed in ethanol in a ratio of 2:1:7, and 0.5% of the polymer dispersant-polyvinylpyrrolidone of the above mixture mass is added to make the solution solid.
  • the content reaches 10% and no sedimentation occurs, and after sufficient agitation and drying, the carbon material can uniformly coat the lithium iron phosphate particles.
  • the dried composite positive electrode material was mixed with fiber pulp and polyvinyl alcohol at 4:5:1 and paper-making to obtain a graphene/active material composite positive electrode paper.
  • Biomass graphene, carbon nanotubes, fiber pulp, and polyvinyl alcohol were mixed and paper-made in a ratio of 1:3:5:1 to obtain a carbon material composite negative electrode paper.
  • the graphene/active material composite positive electrode paper, the separator paper, and the carbon material composite negative electrode paper are sequentially laminated or sequentially laminated, and the positive electrode paper sheet and the negative electrode paper sheet are respectively connected to respective current collectors and then packaged. After vacuuming the reserved port at the time of packaging, an appropriate amount of lithium hexafluorophosphate is injected, and finally the reserved port is closed.
  • the packaged paper battery is milled, and the current collector circuit forms a rechargeable lithium battery.
  • a paper battery 1
  • the fiber pulp is prepared by using nanocellulose as a raw material, and the fiber paper is obtained by a papermaking process and used as a separator paper.
  • the biomass graphene, the carbon nanotubes and the lithium iron phosphate are dispersed in ethanol in a ratio of 2:1:7, and 0.5% of the polymer dispersant-polyvinylpyrrolidone of the above mixture mass is added to make the solution solid.
  • the content reaches 10% and no sedimentation occurs, and after sufficient agitation and drying, the carbon material can uniformly coat the lithium iron phosphate particles.
  • the dried composite positive electrode material was mixed with fiber pulp and polyvinyl alcohol at 4:5:1 and paper-making to obtain a graphene/active material composite positive electrode paper.
  • Biomass graphene, carbon nanotubes, fiber pulp, and polyvinyl alcohol were mixed and paper-made in a ratio of 2:8:75:15 to obtain a carbon material composite negative electrode paper.
  • the graphene/active material composite positive electrode paper, the separator paper, and the carbon material composite negative electrode paper are sequentially laminated or sequentially laminated, and the positive electrode paper sheet and the negative electrode paper sheet are respectively connected to respective current collectors and then packaged. After vacuuming the reserved port at the time of packaging, an appropriate amount of lithium hexafluorophosphate is injected, and finally the reserved port is closed.
  • the packaged paper battery is milled, and the current collector circuit forms a rechargeable lithium battery.
  • a paper battery 1
  • the fiber pulp is prepared by using nanocellulose as a raw material, and the fiber paper is obtained by a papermaking process and used as a separator paper.
  • the biomass graphene, the carbon nanotubes and the lithium iron phosphate are dispersed in ethanol in a ratio of 2:1:7, and 0.5% of the polymer dispersant-polyvinylpyrrolidone of the above mixture mass is added to make the solution solid.
  • the content reaches 10% and no sedimentation occurs, and after sufficient agitation and drying, the carbon material can uniformly coat the lithium iron phosphate particles.
  • the dried composite positive electrode material was mixed with fiber pulp and polyvinyl alcohol at 4:5:1 and paper-making to obtain a graphene/active material composite positive electrode paper.
  • the biomass graphene, the carbon nanotubes, the fiber pulp, and the polyvinyl alcohol were mixed and paper-made in a ratio of 2:3:4:1 to obtain a carbon material composite negative electrode paper.
  • the graphene/active material composite positive electrode paper, the separator paper, and the carbon material composite negative electrode paper are sequentially laminated or sequentially laminated, and the positive electrode paper sheet and the negative electrode paper sheet are respectively connected to respective current collectors and then packaged. After vacuuming the reserved port at the time of packaging, an appropriate amount of lithium hexafluorophosphate is injected, and finally the reserved port is closed.
  • the packaged paper battery is milled, and the current collector circuit forms a rechargeable lithium battery.
  • a paper battery 1
  • the fiber pulp is prepared by using nanocellulose as a raw material, and the fiber paper is obtained by a papermaking process and used as a separator paper.
  • the biomass graphene, carbon fiber and lithium iron phosphate are dispersed in ethanol at a ratio of 2:1:7, and 0.5% of the polymer dispersant-polyvinylpyrrolidone of the above mixture mass is added to achieve a solid content in the solution. 10% and no sedimentation occurred, followed by sufficient agitation and drying, the carbon material can uniformly coat the lithium iron phosphate particles.
  • the dried composite positive electrode material was mixed with fiber pulp and polyvinyl alcohol at 4:5:1 and paper-making to obtain a graphene/active material composite positive electrode paper.
  • the biomass graphene, the carbon fiber, the fiber pulp, and the polyvinyl alcohol were mixed and ground in a ratio of 1:3:5:1 to obtain a carbon material composite negative electrode paper.
  • the graphene/active material composite positive electrode paper, the separator paper, and the carbon material composite negative electrode paper are sequentially laminated or sequentially laminated, and the positive electrode paper sheet and the negative electrode paper sheet are respectively connected to respective current collectors and then packaged. Through the reservation of the package After the vacuum is applied to the mouth, an appropriate amount of lithium hexafluorophosphate is injected, and finally the reserved port is closed. The packaged paper battery is milled, and the current collector circuit forms a rechargeable lithium battery.
  • a paper battery 1
  • the fiber pulp is prepared by using nanocellulose as a raw material, and the fiber paper is obtained by a papermaking process and used as a separator paper.
  • the biomass graphene, carbon fiber and nickel-cobalt-manganese ternary materials are dispersed in ethanol at a ratio of 3:1:6, and 0.5% of the above-mentioned mass of the polymer dispersant-polyvinylpyrrolidone is added to make the solution solid.
  • the content reaches 10% and no sedimentation occurs, and after sufficient agitation and drying, the carbon material can uniformly coat the ternary material particles.
  • the dried composite positive electrode material was mixed with fiber pulp and polyvinyl alcohol in a ratio of 3:6:1 and paper-making to obtain a graphene/active material composite positive electrode paper.
  • the biomass graphene is used as a raw material, and the polymer dispersant is dissolved in water to obtain a slurry having a solid content of 12%.
  • the slurry was sprayed on the surface of the graphene/active material composite positive electrode sheet and dried to obtain a surface carbon current collecting layer.
  • the biomass graphene, the carbon fiber, the fiber pulp, and the polyvinyl alcohol were mixed and ground in a ratio of 1:3:5:1 to obtain a carbon material composite negative electrode paper.
  • the graphene/active material composite positive electrode paper, the separator paper, and the carbon material composite negative electrode paper are sequentially laminated or sequentially laminated, and the positive electrode paper collecting layer and the negative electrode paper sheet are respectively connected to respective current collectors and then packaged. After vacuuming the reserved port at the time of packaging, an appropriate amount of lithium hexafluorophosphate is injected, and finally the reserved port is closed.
  • the packaged paper battery is milled, and the current collector circuit forms a rechargeable lithium battery.
  • a paper battery 1
  • Paper is made from nanocellulose as raw material, and nanocellulose paper is obtained as separator paper.
  • the separator paper has high flexibility and strength, and has high porosity, which is suitable for adsorption of electrolyte.
  • Graphene was mixed with carbon fiber, nanocellulose pulp, and polyvinyl alcohol in a ratio of 1:4:4:1 to obtain paper, and a porous carbon material conductive paper structure was obtained as a positive electrode paper.
  • porous carbon material conductive paper, the separator paper, and the lithium sheet are sequentially laminated or sequentially laminated, and the positive electrode paper collecting layer and the negative electrode lithium sheet are respectively connected to respective current collectors and then packaged. After vacuuming the reserved port at the time of packaging, an appropriate amount of lithium hexafluorophosphate is injected, and finally the reserved port is closed.
  • the packaged paper battery is milled, and the current collector circuit forms a disposable lithium battery.
  • a paper battery 1
  • Paper is made from nanocellulose as raw material, and nanocellulose paper is obtained as separator paper.
  • the separator paper has high flexibility and strength, and has high porosity, which is suitable for adsorption of electrolyte.
  • Graphene was mixed with carbon fiber, nanocellulose pulp, and polyvinyl alcohol in a ratio of 2:3:4:1 to obtain a porous carbon material conductive paper structure.
  • the conductive paper was then immersed in a silver chloride solution and then dried to serve as a positive electrode.
  • the silver chloride porous carbon material conductive paper, the separator paper, and the magnesium sheet are sequentially laminated or sequentially laminated, and the positive electrode paper collecting layer and the negative electrode magnesium sheet are respectively connected to the respective current collectors and then packaged. After vacuuming the reserved port at the time of packaging, an appropriate amount of magnesium chloride solution is injected, and finally the reserved port is closed.
  • the packaged paper battery is milled, and the current collector circuit forms a disposable paper magnesium battery.
  • the magnesium sheet of this embodiment can be replaced with a magnesium alloy sheet, and the substitution has little effect on the performance of the battery.
  • a paper battery 1
  • the fiber pulp is prepared by using nanocellulose as a raw material, and the fiber paper is obtained by a papermaking process and used as a separator paper.
  • Biomass graphene, carbon nanotubes and lithium cobalt oxide are dispersed in ethanol at a ratio of 2:1:7 and a certain amount of polymer dispersant is added to make the solid content in the solution reach 10% and no sedimentation occurs.
  • the carbon material can then uniformly coat the lithium iron phosphate particles after thorough agitation and drying.
  • the dried composite positive electrode material is mixed with the fiber pulp and the modified starch according to 4:5:1 and paper-making to obtain a graphene/active material composite positive electrode paper.
  • the biomass graphene, the carbon nanotubes, the fiber pulp, and the modified starch were mixed and paper-made in a ratio of 1:3:5:1 to obtain a carbon material composite negative electrode paper.
  • the graphene/active material composite positive electrode paper, the separator paper, and the carbon material composite negative electrode paper are sequentially laminated or sequentially laminated, and the positive electrode paper sheet and the negative electrode paper sheet are respectively connected to respective current collectors and then packaged. After vacuuming the reserved port at the time of packaging, an appropriate amount of lithium hexafluorophosphate is injected, and finally the reserved port is closed.
  • the packaged paper battery is milled, and the current collector circuit forms a rechargeable lithium battery.
  • a paper battery 1
  • the fiber pulp is prepared by using nanocellulose as a raw material, and the fiber paper is obtained by a papermaking process and used as a separator paper.
  • the biomass graphene, carbon nanotubes and lithium manganate are dispersed in ethanol at a ratio of 2:1:7 and a certain amount of polymer dispersant is added to make the solid content in the solution reach 10% and no sedimentation occurs.
  • the carbon material can then uniformly coat the lithium iron phosphate particles after thorough agitation and drying.
  • the dried composite positive electrode material was mixed with fiber pulp and anionic polyacrylamide at 4:5:1 and paper-making to obtain a graphene/active material composite positive electrode paper.
  • the biomass graphene, the carbon nanotubes, the fiber pulp, and the anionic polyacrylamide were mixed at a ratio of 1:3:5:1 and paper-made to obtain a carbon material composite negative electrode paper.
  • the graphene/active material composite positive electrode paper, the separator paper, and the carbon material composite negative electrode paper are sequentially laminated or sequentially laminated, and the positive electrode paper sheet and the negative electrode paper sheet are respectively connected to respective current collectors and then packaged. After vacuuming the reserved port at the time of packaging, an appropriate amount of lithium hexafluorophosphate is injected, and finally the reserved port is closed. Milling the packaged paper battery, The current collector access circuit forms a rechargeable lithium battery.
  • a paper battery 1
  • the fiber pulp is prepared by using nanocellulose as a raw material, and the fiber paper is obtained by a papermaking process and used as a separator paper.
  • the biomass graphene, carbon nanotubes and lithium iron phosphate are dispersed in ethanol at a ratio of 2:1:7 and a certain amount of polymer dispersant is added to make the solid content in the solution reach 10% and no sedimentation occurs.
  • the carbon material can then uniformly coat the lithium iron phosphate particles after thorough agitation and drying.
  • the dried composite positive electrode material was mixed with fiber pulp and carboxymethyl cellulose according to 4:5:1 and paper-making to obtain a graphene/active material composite positive electrode paper.
  • the biomass graphene, the carbon nanotubes, the fiber pulp, and the carboxymethyl cellulose were mixed at a ratio of 1:3:5:1 and paper-made to obtain a carbon material composite negative electrode paper.
  • the graphene/active material composite positive electrode paper, the separator paper, and the carbon material composite negative electrode paper are sequentially laminated or sequentially laminated, and the positive electrode paper sheet and the negative electrode paper sheet are respectively connected to respective current collectors and then packaged. After vacuuming the reserved port at the time of packaging, an appropriate amount of lithium hexafluorophosphate is injected, and finally the reserved port is closed.
  • the packaged paper battery is milled, and the current collector circuit forms a rechargeable lithium battery.
  • a heat-generating conductive paper
  • the biomass graphene, the carbon nanotubes, the fiber pulp, and the polyvinyl alcohol were mixed and ground in a ratio of 1:3:5:1 to obtain a carbon material composite conductive paper. Electrodes and wires were printed on the surface of the conductive paper using copper paste (silver paste). Then the heat paper is finished. Finally, the heat-generating paper is integrally packaged using an insulating layer (material such as PET).
  • the heating paper obtained in this embodiment is light in weight, good in flexibility, and is suitable for working at a small working voltage, and the working temperature is suitable for the human body to bear. It can be embedded in clothing and body care wearables, and is powered by 3.7V. By adjusting the voltage output, the temperature can be controlled at 30-60 degrees Celsius.
  • Example 1 4mAh/cm2 87%
  • Example 2 3.7mAh/cm2 89%
  • Example 3 4.1mAh/cm2 85%
  • Example 4 4mAh/cm2 85%
  • Example 5 5.5mAh/cm2 80%
  • Example 6 38mAh/cm2 Disposable battery can not be charged
  • Example 7 42mAh/cm2 Disposable battery can not be charged
  • Example 8 3.2mAh/cm2 90%
  • Example 9 2.5mAh/cm2 89%
  • Example 10 3.8mAh/cm2 82% Comparison 1 2.5-5mAh/cm2 Disposable battery can not be charged
  • Comparison 1 is: Israel Powerpaper company paper battery patent HK20010101229, the electrode materials used are zinc and manganese dioxide, and the electrolyte is zinc chloride.
  • Test method for specific capacity The charge and discharge capacity was tested using a conventional blue battery test system.
  • Test method for cycle efficiency A conventional blue battery test system is used.

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Abstract

The present invention provides a paper electrode composite material, and a paper electrode, conductive graphene sheet, and paper battery, and an application thereof. The paper electrode composite material mainly comprises 5-10% by weight of a carbon material, 34-57% by weight of a paper pulp, and 6-9% by weight of an auxiliary agent. The paper electrode mainly comprises 30-50% by weight of a positive electrode active material and 50-70% by weight of the composite material. The conductive graphene paper mainly comprises 10-50% by weight of a nanocarbon material, 40-75% by weight of the paper pulp, and 8-18% of the auxiliary agent. The nanocarbon material comprises at least a graphene. The auxiliary agent is a composition comprising at least one or more of the following: a modified starch, anionic polyacrylamide, poly(vinyl alcohol), and carboxymethyl cellulose. The invention can be applied to the technical field of paper batteries and provides advantages such as improved specific capacity, stable battery performance, longer battery life, and the like.

Description

一种用于纸电极的复合材料、纸电极、石墨导电纸、纸电池及其应用Composite material for paper electrode, paper electrode, graphite conductive paper, paper battery and application thereof
本申请要求于2016年04月01日提交中国专利局、申请号为CN 201610206309.5、发明名称为“石墨烯导电纸及纸电池及其应用”以及2016年04月01日提交中国专利局、申请号为CN201610203943.3、发明名称为“用于纸电极的复合材料及其制成的纸电极、纸电池”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application is required to be submitted to the China Patent Office on April 1, 2016, the application number is CN 201610206309.5, the invention name is “graphene conductive paper and paper battery and its application”, and the Chinese Patent Office and application number are submitted on April 1, 2016. The priority of the Chinese patent application entitled "Composite material for paper electrodes and paper electrodes and paper batteries made thereof" is hereby incorporated by reference.
技术领域Technical field
本发明涉及导电材料领域，具体而言，涉及用于纸电极的复合材料、纸电极、纸电池、石墨导电纸、纸电池及其应用。The present invention relates to the field of conductive materials, and in particular to composite materials for paper electrodes, paper electrodes, paper batteries, graphite conductive paper, paper batteries, and applications thereof.
背景技术Background technique
电池的重量、不可弯折、容量、寿命等问题一直阻碍着电子产品的进一步轻便化。纸电池有助于减轻电子产品的重量，延长产品寿命，并赋予电池一定的柔韧性，起到与柔性轻便电子产品相互推动的作用。The weight, non-bending, capacity, and longevity of the battery have always hindered the further portability of electronic products. Paper batteries help to reduce the weight of electronic products, extend the life of the product, and give the battery a certain degree of flexibility, which promotes the interaction with flexible and lightweight electronic products.
利用成熟的纸张技术，将可传导的纸用作集电器和电极，提供了一种低成本、轻质且高效的能源储备的思路。目前全世界仅美国、以色列、芬兰、瑞典等几个国家在本领域有一定的研发成果。纸电池主要是以纤维纸为载体，用纳米材料做成的墨水进行涂敷或印刷，构成电池或超级电容器。这种纸电池可以剪裁、弯曲，对环境友好且成本不高。其应用领域涉及射频识别器(RFID)、电子标签、智能卡等，潜在应用领域则涉及到手机、手提电脑等诸多电子产品。Using proven paper technology to use conductive paper as a current collector and electrode provides a low-cost, lightweight, and efficient energy reserve. At present, only the United States, Israel, Finland, Sweden and other countries in the world have certain research and development achievements in this field. The paper battery is mainly coated with fiber paper as a carrier and coated or printed with ink made of nano material to form a battery or a super capacitor. This paper battery can be cut, bent, environmentally friendly and inexpensive. Its application fields include radio frequency identification (RFID), electronic tags, smart cards, etc., and potential applications include mobile phones, laptops and many other electronic products.
导电活性炭、碳纳米管、石墨烯等纳米碳材料由于具有优异的导电性和稳定的物化性能，在纸电池研究中受到越来越多的关注，尤其是石墨烯。例如CN103966907A、CN102619128B、CN102169999B等专利申请都研究了纳米碳材料在纸电池或纸电极中的应用，这些技术方案都只是将纳米碳材料与纸浆简单地混合在一起制成纸电极，或者是还加入电极活性材料，并没有考虑纳米碳材料与纸浆的混合效果对纸电池导电性能的影响，导致电极的导电性能提高不明显，无法充分发挥纳米碳材料的优越性。Nano-carbon materials such as conductive activated carbon, carbon nanotubes, and graphene have attracted more and more attention in paper battery research due to their excellent electrical conductivity and stable physical and chemical properties, especially graphene. For example, CN103966907A, CN102619128B, CN102169999B and other patent applications have studied the application of nano-carbon materials in paper batteries or paper electrodes. These technical solutions simply mix nano-carbon materials with pulp to make paper electrodes, or add them. The electrode active material does not consider the influence of the mixing effect of the nano carbon material and the pulp on the electrical conductivity of the paper battery, and the conductivity of the electrode is not improved significantly, and the superiority of the nano carbon material cannot be fully utilized.
有鉴于此，特提出本发明。In view of this, the present invention has been specifically proposed.
发明内容Summary of the invention
本发明的之一目的在于提供一种用于纸电极的复合材料，所述的复合材料能够提高纸电极的使用寿命、导电性和使用寿命。It is an object of the present invention to provide a composite material for paper electrodes which is capable of improving the service life, electrical conductivity and service life of paper electrodes.
本发明的另一目的在于提供一种石墨烯导电纸，所述的石墨烯导电纸既可以作为纸电池的正极，也可以作为纸电池的负极，应用于纸电池领域具有提高比容量、稳定电池性能、提高电池寿命等优点。 Another object of the present invention is to provide a graphene conductive paper, which can be used as a positive electrode of a paper battery or as a negative electrode of a paper battery, and has a specific capacity and a stable battery in the field of paper batteries. Performance, improved battery life and other advantages.
本发明的又一目的在于提供一种纸电极，所述的纸电极具有性能稳定、寿命长等优点。It is still another object of the present invention to provide a paper electrode which has the advantages of stable performance, long life, and the like.
本发明的又一目的在于提供一种纸电池，所述的纸电池具有电池容量高、性能稳定、寿命长等优点。It is still another object of the present invention to provide a paper battery which has the advantages of high battery capacity, stable performance, long life, and the like.
本发明的再一目的在于提供了石墨烯导电纸的应用，该应用非常广泛，包括用于制作可穿戴器件或服饰的电源，或者用于制作导电面膜的电源等，本发明对其应用并不限制。A further object of the present invention is to provide an application of graphene conductive paper, which is very widely used, including a power source for manufacturing a wearable device or clothing, or a power source for producing a conductive mask, etc., and the present invention is not applied thereto. limit.
为了实现本发明的上述目的中的至少一个，特采用以下技术方案：In order to achieve at least one of the above objects of the present invention, the following technical solutions are employed:
一种用于纸电极的复合材料，主要由碳材料、纸浆和助剂以5-10：34-57：6-9的质量比制成；所述碳材料至少包含有石墨烯，所述助剂为选自由改性淀粉、阴离子聚丙烯酰胺、聚乙烯醇和羧甲基纤维素组成的组中的一种或多种。A composite material for a paper electrode, mainly composed of a carbon material, a pulp and an auxiliary agent in a mass ratio of 5-10:34-57:6-9; the carbon material containing at least graphene, the auxiliary The agent is one or more selected from the group consisting of modified starch, anionic polyacrylamide, polyvinyl alcohol, and carboxymethyl cellulose.
与现有技术相比，本发明的复合材料主要从化学组成上优化了助剂的添加类型以及其与纳米碳材料、纸浆的配比，从而改善了对纸电极的包覆作用。Compared with the prior art, the composite material of the invention mainly optimizes the addition type of the auxiliary agent and its ratio with the nano carbon material and the pulp, thereby improving the coating effect on the paper electrode.
具体地，首先与现有技术相比，本发明的复合材料具有更好的包裹性，一方面能够有效限制电极活性材料(尤其是正极活性材料)的体积膨胀，从而提高了电极的使用寿命，固定导电通路；另一方面由于二维材料—石墨烯的存在，使电极活性材料与复合材料实现面接触，从而大大提高了活性材料的导电性。Specifically, firstly, compared with the prior art, the composite material of the invention has better encapsulation, and on the one hand, can effectively limit the volume expansion of the electrode active material (especially the positive electrode active material), thereby improving the service life of the electrode. The conductive path is fixed; on the other hand, due to the existence of the two-dimensional material-graphene, the electrode active material is in surface contact with the composite material, thereby greatly improving the conductivity of the active material.
其次，本发明添加特定种类、特定配比的助剂，将包覆作用对纸电极的不利影响降低到较低的水平，甚至零水平。Secondly, the present invention adds a specific type of specific ratio of auxiliary agents to reduce the adverse effects of the coating on the paper electrode to a lower level or even a zero level.
另外，本发明通过优化各原料之间的配比避免了静电等问题，当包覆纸电极时能够提高其机械强度和化学稳定性。Further, the present invention avoids problems such as static electricity by optimizing the ratio between the respective raw materials, and can improve mechanical strength and chemical stability when coating the paper electrode.
此外，由于本发明的复合材料能够稳定纸电极的充放电性能，因此本发明制成的纸电极寿命更长，制成的纸电池的电容量损耗速度慢。Further, since the composite material of the present invention can stabilize the charge and discharge performance of the paper electrode, the paper electrode produced by the present invention has a longer life, and the battery capacity of the produced paper battery is slow.
上述复合材料主要用于正电极，包覆电极时需要加入相应的活性材料，包覆的方法有多种，既可以将复合材料的所有原料和活性材料一起混合造纸，也可以采用其它可行的方法。本发明对其它包覆方法及其它用途并不做限制。The above composite material is mainly used for the positive electrode, and the corresponding active material needs to be added when coating the electrode, and there are various methods for coating, and all the raw materials of the composite material and the active material can be mixed and made by paper, or other feasible methods can be adopted. . The present invention is not limited to other coating methods and other uses.
优选地，对于上述复合材料，所述纳米碳材料中石墨烯的含量优选为65wt％-75wt％。Preferably, for the above composite material, the content of graphene in the nanocarbon material is preferably from 65 wt% to 75 wt%.
石墨烯的含量不宜过低，否则电容量不理想；也不宜过高，否则会加大分散难度，提高原料成本。The content of graphene should not be too low, otherwise the capacity is not ideal; it should not be too high, otherwise it will increase the difficulty of dispersion and increase the cost of raw materials.
为了实现本发明的上述目的，特采用以下技术方案：In order to achieve the above object of the present invention, the following technical solutions are adopted:
一种石墨烯导电纸，主要由纳米碳材料、纸浆和助剂以10-50％：40-75％：8-18％的质量百分比制成；所述纳米碳材料至少包含有石墨烯，所述助剂为选自由改性淀粉、阴离子聚丙烯酰胺、聚乙烯醇和羧甲基纤维素组成的组中的一种或多种。A graphene conductive paper mainly made of nano carbon material, pulp and auxiliary agent in a mass percentage of 10-50%: 40-75%: 8-18%; the nano carbon material contains at least graphene, The auxiliary agent is one or more selected from the group consisting of modified starch, anionic polyacrylamide, polyvinyl alcohol, and carboxymethyl cellulose.
与现有技术相比，本发明的上述石墨烯导电纸主要从化学组成上优化了助剂 的添加类型以及其与纳米碳材料、纸浆的配比，从而改善了导电综合性能。Compared with the prior art, the above graphene conductive paper of the present invention mainly optimizes the chemical composition from the auxiliary agent. The type of addition and its ratio to nano-carbon materials and pulp improve the electrical conductivity.
具体地，首先与现有技术相比，本发明的导电纸具有更好的导电性能，通过添加特定的助剂改善纳米碳材料的分散性以及晶粒的粒度，从而使导电纸具有更均匀的导电性以及电阻可调性，此处的“电阻可调性”是指当加入的助剂种类不同或者含量不同时，导电纸的电阻值不同，这就可以保证导电纸可用于不同的领域，例如电阻较低的导电纸可用于电加热(通过低电阻产生高电流加热物体)材料领域，电阻较高的导电纸可用于低电流传输材料，上述导电纸的电阻在20-2000Ω/sq以内可调节。另外，本发明通过优化各原料之间的配比避免了静电等问题，同时提高了导电纸的机械强度和化学稳定性。Specifically, first, the conductive paper of the present invention has better electrical conductivity than the prior art, and the dispersibility of the nano carbon material and the grain size of the crystal grains are improved by adding a specific auxiliary agent, thereby making the conductive paper more uniform. Conductivity and resistance adjustability, "resistance adjustability" here means that when the kinds of additives added are different or the content is different, the resistance values of the conductive paper are different, which can ensure that the conductive paper can be used in different fields. For example, conductive paper with lower resistance can be used for electric heating (heating objects with high electric resistance by low resistance). The conductive paper with higher resistance can be used for low current transmission materials. The resistance of the above conductive paper can be within 20-2000 Ω/sq. Adjustment. In addition, the present invention avoids problems such as static electricity by optimizing the ratio between the respective raw materials, and at the same time improves the mechanical strength and chemical stability of the conductive paper.
其次也是更重要的，本发明选用改性淀粉起粘结作用，阴离子聚丙烯酰胺、聚乙烯醇、羧甲基纤维素这些特定的助剂提高了石墨烯的分散效果，使该导电纸既可以用作纸电池的负极，也可以用作正极；并且其具有比现有电极更大的储存对立的电极活性物质的容量，因而对应的电池也具有更大的电容量；并且由于本发明的导电纸比现有电极的具有更稳定的充放电性能，因此本发明制成的电池寿命更长，即电容量的损耗速度慢。Secondly and more importantly, the present invention selects modified starch for bonding, and specific additives such as anionic polyacrylamide, polyvinyl alcohol and carboxymethyl cellulose improve the dispersion effect of graphene, so that the conductive paper can be Used as a negative electrode of a paper battery, can also be used as a positive electrode; and it has a larger capacity for storing opposite electrode active materials than existing electrodes, and thus the corresponding battery also has a larger capacitance; and due to the conductive of the present invention Paper has more stable charge and discharge performance than existing electrodes, so the battery produced by the present invention has a longer life, that is, the loss rate of the electric capacity is slow.
另外，上述导电纸作为正极纸或负极纸使用时，其对应的另一电极可采用任意可用的电极材料。Further, when the above conductive paper is used as a positive electrode paper or a negative electrode paper, the other electrode corresponding thereto may be any available electrode material.
优选地，对于上述石墨烯导电纸，所述纳米碳材料中石墨烯的重量比为20％-40％。Preferably, for the above graphene conductive paper, the weight ratio of graphene in the nanocarbon material is 20% to 40%.
石墨烯的含量不宜过低，否则电容量不理想；也不宜过高，否则会加大分散难度，提高原料成本。The content of graphene should not be too low, otherwise the capacity is not ideal; it should not be too high, otherwise it will increase the difficulty of dispersion and increase the cost of raw materials.
优选地，对于上述石墨烯导电纸，所述纳米碳材料、所述纸浆和所述助剂的质量百分比分别为：10-40％、50-75％、10-15％。Preferably, for the above graphene conductive paper, the mass percentages of the nano carbon material, the pulp and the auxiliary agent are respectively 10-40%, 50-75%, 10-15%.
该组成的导电纸更适宜用作电池的负极。The conductive paper of this composition is more suitably used as a negative electrode of a battery.
优选地，对于上述石墨烯导电纸，所述纳米碳材料、所述纸浆和所述助剂的质量百分比分别为：30-50％、40-56％、10-14％。Preferably, for the above graphene conductive paper, the mass percentages of the nano carbon material, the pulp and the auxiliary agent are respectively 30-50%, 40-56%, 10-14%.
该组成的导电纸更适宜用作电池的正极。The conductive paper of this composition is more suitably used as the positive electrode of the battery.
上文所述的本发明的所有导电纸都可以采用简单的制备方法：将所有原料混合再造纸，所述的造纸工序主要指混合和干燥的过程。当然，也可以采用其它可行的制作方法。All of the conductive papers of the present invention described above can be prepared by a simple preparation method: mixing all the raw materials and making paper, and the papermaking process mainly refers to a mixing and drying process. Of course, other feasible production methods can also be used.
本发明的助剂优选改性淀粉和聚乙烯醇。The adjuvant of the present invention is preferably a modified starch and a polyvinyl alcohol.
本发明所述的石墨烯包括石墨烯纳米片层和石墨烯，进一步包括生物质石墨烯纳米片 层和生物质石墨烯。The graphene of the present invention comprises a graphene nanosheet layer and graphene, and further comprises a biomass graphene nanosheet. Layer and biomass graphene.
本发明所述的石墨烯可通过不同制备方法得到，例如机械剥离法、外延生长法、化学气相沉淀法，石墨氧化还原法，还可以是通过对生物质资源水热碳化法，以及现有技术中其它方法制备的石墨烯。但是，无论哪种方法都很难实现大规模制备得到严格意义理论上的石墨烯，例如现有技术制备得到的石墨烯中会存在某些杂质元素、碳元素的其它同素异形体或层数非单层甚至多层的石墨烯结构(例如3层、5层、10层、20层等)，本发明所利用的石墨烯也包括上述非严格意义理论上的石墨烯。The graphene of the present invention can be obtained by different preparation methods, such as mechanical stripping method, epitaxial growth method, chemical vapor deposition method, graphite redox method, hydrothermal carbonization method for biomass resources, and prior art. Graphene prepared by other methods. However, it is difficult to achieve large-scale preparation of graphene in a strictly theoretical manner by any method. For example, some impurity elements, other allotropes or layers of carbon elements may be present in the graphene prepared by the prior art. Non-monolayer or even multi-layer graphene structures (for example, 3 layers, 5 layers, 10 layers, 20 layers, etc.), the graphene utilized in the present invention also includes the above-mentioned non-strict theoretical graphene.
石墨烯纳米片层可采用济南圣泉公司工艺，以农林废弃物为主要原料，通过水解、催化处理、热处理等步骤获得具有优良导电性质的多孔生物质石墨烯复合物，其主要特征为所含石墨烯层数为1～10层之间，非碳非氧元素含量为0.5wt％～6wt％。The graphene nanosheet layer can adopt the process of Jinan Shengquan Company, and the porous biomass graphene composite with excellent conductive properties is obtained by the steps of hydrolysis, catalytic treatment and heat treatment with the agricultural and forestry waste as the main raw material, and its main feature is contained. The number of graphene layers is between 1 and 10 layers, and the content of non-carbon non-oxygen elements is from 0.5% by weight to 6% by weight.
上述复合材料及石墨烯导电纸还可以进一步改进，以改善其效果：The above composite materials and graphene conductive paper can be further improved to improve the effect:
优选地，所述纳米碳材料还至少包含碳纤维和碳纳米管中的一种。Preferably, the nanocarbon material further comprises at least one of carbon fibers and carbon nanotubes.
增加碳纤维或碳纳米管之后，同样可以形成导电网络来增加复合材料及导电纸的导电性，还可以减少石墨烯的用量，以降低原料成本。After adding carbon fiber or carbon nanotubes, a conductive network can also be formed to increase the electrical conductivity of the composite material and the conductive paper, and the amount of graphene can be reduced to reduce the raw material cost.
优选地，所述纸浆为纳米纤维纸浆。Preferably, the pulp is nanofiber pulp.
纳米级别的纤维纸浆与石墨烯的相容性更好，且对石墨烯的分散性更好。Nano-grade fiber pulp has better compatibility with graphene and better dispersibility for graphene.
为了实现本发明的上述目的中的至少一个，特采用以下技术方案：In order to achieve at least one of the above objects of the present invention, the following technical solutions are employed:
一种纸电极，主要由正极活性材料和上文所述的复合材料制成，且两者的质量百分比分别为30-50％，50-70％。A paper electrode mainly composed of a positive electrode active material and a composite material as described above, and the mass percentage of both is 30-50%, 50-70%, respectively.
如上文所述，该纸电极经复合材料包覆后，导电性能更稳定，使用寿命延长。As described above, after the paper electrode is coated with the composite material, the electrical conductivity is more stable and the service life is prolonged.
该纸电极可以采用简单的制备方法：将所有原料混合再造纸，所述的造纸工序主要指混合和干燥的过程。当然，也可以采用其它可行的制作方法。The paper electrode can be prepared by a simple preparation method in which all the raw materials are mixed and then subjected to papermaking, and the papermaking process mainly refers to a process of mixing and drying. Of course, other feasible production methods can also be used.
为了提高分散性，可以适当加入分散剂，例如聚丙烯酰胺等高分子分散剂。In order to improve dispersibility, a dispersing agent such as a polymer dispersing agent such as polyacrylamide may be appropriately added.
优选地，所述正极活性材料为选自由锰酸锂、钴酸锂、磷酸铁锂、磷酸亚铁锂和三元镍钴锰组成的组中的一种或多种。Preferably, the cathode active material is one or more selected from the group consisting of lithium manganate, lithium cobaltate, lithium iron phosphate, lithium iron phosphate, and ternary nickel cobalt manganese.
优选地，所述碳材料、所述纸浆、所述助剂和所述正极活性材料的质量百分比分别为：5-10％，34-57％，6-9％，30-50％。Preferably, the mass percentage of the carbon material, the pulp, the auxiliary agent and the positive active material are: 5-10%, 34-57%, 6-9%, 30-50%, respectively.
为了实现本发明的上述目的中的至少一个，特采用以下技术方案：In order to achieve at least one of the above objects of the present invention, the following technical solutions are employed:
一种纸电池，包括主要由上文所述的纸电极组成的正极纸。A paper battery comprising a positive paper mainly composed of the paper electrodes described above.
本发明对该纸电池所用的负极纸不作特别限定，只要与上述正极纸搭配可组成有效的电池即可。例如，采用以下负极纸：所述负极纸主要由所述碳材料、所述纸浆和所述助剂以10-50％：40-75％：8-18％的质量百分比制成，负极纸更进一步的配比为10-40％：50-75％： 10-15％。The negative electrode paper used in the paper battery of the present invention is not particularly limited, and may be an effective battery if it is combined with the above positive electrode paper. For example, the following negative paper is used: the negative paper is mainly made of the carbon material, the pulp and the auxiliary agent in a mass percentage of 10-50%: 40-75%: 8-18%, and the negative paper is further The further ratio is 10-40%: 50-75%: 10-15%.
为了实现本发明的上述目的中的至少一个，特采用以下技术方案：In order to achieve at least one of the above objects of the present invention, the following technical solutions are employed:
一种石墨烯纸电池，所述石墨烯纸电池的正极纸或负极纸中的一个主要由上文所述的石墨烯导电纸制成。A graphene paper battery, one of a positive or negative paper of the graphene paper battery is mainly made of the graphene conductive paper described above.
上述石墨烯纸电池涉及了两种类型：一种是以本发明的导电纸作为正极，另一种是以本发明的导电纸作为负极；如上文所述，这两种电池都具有电池容量高、性能稳定、寿命长的优点。The above graphene paper batteries are of two types: one is a conductive paper of the present invention as a positive electrode, and the other is a conductive paper of the present invention as a negative electrode; as described above, both of the batteries have a high battery capacity. The advantages of stable performance and long life.
其中，当所述正极纸主要由所述石墨烯导电纸制成时，所述负极纸为电势低于正极纸的金属箔片或涂覆于基体的金属涂层；所述金属箔片或所述金属涂层优选为金属锂或镁。当然活性材料不仅限于这两种，只要能够实现可逆的充放电功能即可。Wherein, when the positive electrode paper is mainly made of the graphene conductive paper, the negative electrode paper is a metal foil having a lower potential than the positive electrode paper or a metal coating applied to the substrate; the metal foil or the metal foil The metal coating is preferably metallic lithium or magnesium. Of course, the active material is not limited to these two types as long as a reversible charge and discharge function can be achieved.
当所述正、负极纸主要由所述石墨烯导电纸制成时，所述正极纸至少还含有正极活性材料；当然活性材料不仅限于这几种，只要能够实现可逆的充放电功能即可。其中，所述正极活性材料优选为锰酸锂、钴酸锂、磷酸铁锂、磷酸亚铁锂和三元镍钴锰中的一种或多种，这些材料与本发明导电纸的电位差较大，可以提高电池容量。When the positive and negative papers are mainly made of the graphene conductive paper, the positive electrode paper further contains at least a positive electrode active material; of course, the active material is not limited to these types as long as a reversible charge and discharge function can be achieved. Wherein, the positive electrode active material is preferably one or more of lithium manganate, lithium cobaltate, lithium iron phosphate, lithium iron phosphate, and ternary nickel cobalt manganese, and the potential difference between these materials and the conductive paper of the present invention is Large, can increase battery capacity.
通常，上述纸电池或者上述石墨烯纸电池还设置有隔膜纸和电解液，即所述纸电池或者石墨烯纸电池由所述正极纸、所述隔膜纸和所述负极纸依次叠压而成，并且所述正极纸、所述隔膜纸和所述负极纸浸渍于所述电解液中并封装。隔膜纸可采用任意材料，只要起隔离正极和负极的作用即可。电解液主要根据正极和负极的材料来选择，要保证充放电过程中发生的化学反应是可逆的。Generally, the above paper battery or the above graphene paper battery is further provided with a separator paper and an electrolyte, that is, the paper battery or the graphene paper battery is sequentially laminated from the positive paper, the separator paper and the negative paper. And the positive electrode paper, the separator paper, and the negative electrode paper are immersed in the electrolytic solution and encapsulated. The separator paper can be any material as long as it functions to isolate the positive electrode and the negative electrode. The electrolyte is mainly selected according to the materials of the positive electrode and the negative electrode, and it is necessary to ensure that the chemical reaction occurring during charging and discharging is reversible.
在制作上述纸电池的成品时，为了正极纸、隔膜纸和负极纸都吸附有足够的电解液，又避免电解液过量，可以将纸电池封装起来，并使极耳暴露在外，再向封装体内注入电解液。本发明对此封装并不作限制。In the production of the above-mentioned paper battery, in order to adsorb sufficient electrolyte for the positive paper, the separator paper and the negative paper, and avoid excessive electrolyte, the paper battery can be packaged, and the tabs are exposed and then exposed to the package. Inject the electrolyte. The present invention is not limited to this package.
进一步地，所述电解液为六氟磷酸锂、高氯酸锂、四氟硼酸锂中的一种或多种。Further, the electrolyte is one or more of lithium hexafluorophosphate, lithium perchlorate, and lithium tetrafluoroborate.
另外，本发明所用的正极纸上还可以设置碳集流层。优选的，当所述负极纸由所述石墨烯导电纸制成时，所述正极纸的表面还设有碳集流层。Further, a carbon current collector layer may be further provided on the positive electrode paper used in the present invention. Preferably, when the negative paper is made of the graphene conductive paper, the surface of the positive paper is further provided with a carbon current collecting layer.
设置碳集流层可以提高电极的导电性，从而提高电池的充放电速率，优选采用喷涂的方式在正极纸的表面形成碳集流层。The carbon current collecting layer can improve the conductivity of the electrode, thereby increasing the charge and discharge rate of the battery, and preferably forming a carbon current collecting layer on the surface of the positive electrode by spraying.
与现有技术相比，本发明的有益效果至少包括：Compared with the prior art, the beneficial effects of the present invention include at least:
(1)采用复合材料提高纸电极(尤其是正电极)的使用寿命、稳定性和导电性能；(1) using composite materials to improve the service life, stability and electrical conductivity of paper electrodes (especially positive electrodes);
(2)提供了一种容量高、性能稳定、寿命长的纸电池； (2) Providing a paper battery with high capacity, stable performance and long service life;
(3)提供了一种导电性更均匀、电阻可调、无静电问题、机械强度和化学稳定性更高、能提高电池容量和使用寿命的导电纸；(3) Providing a conductive paper having more uniform conductivity, adjustable electrical resistance, no static problem, higher mechanical strength and chemical stability, and improved battery capacity and service life;
(4)拓宽了导电纸和纸电池的应用领域，为导电纸和纸电池的工业化应用开辟了新途径。(4) Broadening the application fields of conductive paper and paper batteries, opening up new avenues for the industrial application of conductive paper and paper batteries.
具体实施方式detailed description
下面将结合实施例对本发明的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本发明，而不应视为限制本发明的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。The embodiments of the present invention will be described in detail below with reference to the accompanying drawings, but the present invention is to be construed as illustrative only. Those who do not specify the specific conditions in the examples are carried out according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are conventional products that can be obtained by commercially available purchase.
实施例1Example 1
一种纸电池：A paper battery:
以纳米纤维素为原料，制备纤维纸浆，再通过造纸工艺获得纤维纸并作为隔膜纸。The fiber pulp is prepared by using nanocellulose as a raw material, and the fiber paper is obtained by a papermaking process and used as a separator paper.
将生物质石墨烯、碳纳米管和磷酸亚铁锂，按照2：1：7的比例分散在乙醇中，并加入0.5％于以上混合物质量的高分子分散剂-聚乙烯吡咯烷酮，使溶液中固含量达到10％且无沉降现象发生，随后经过充分搅拌和干燥，碳材料可将磷酸亚铁锂颗粒均匀包覆。将干燥好的复合正极材料与纤维纸浆、聚乙烯醇按照4：5：1进行混合并造纸，获得石墨烯/活性材料复合正极纸。The biomass graphene, the carbon nanotubes and the lithium iron phosphate are dispersed in ethanol in a ratio of 2:1:7, and 0.5% of the polymer dispersant-polyvinylpyrrolidone of the above mixture mass is added to make the solution solid. The content reaches 10% and no sedimentation occurs, and after sufficient agitation and drying, the carbon material can uniformly coat the lithium iron phosphate particles. The dried composite positive electrode material was mixed with fiber pulp and polyvinyl alcohol at 4:5:1 and paper-making to obtain a graphene/active material composite positive electrode paper.
将生物质石墨烯、碳纳米管、纤维纸浆、聚乙烯醇按照1：3：5：1的比例混合并造纸，获得碳材料复合负极纸。Biomass graphene, carbon nanotubes, fiber pulp, and polyvinyl alcohol were mixed and paper-made in a ratio of 1:3:5:1 to obtain a carbon material composite negative electrode paper.
按照石墨烯/活性材料复合正极纸，隔膜纸，碳材料复合负极纸的顺序依次层叠或依次反复层叠，正极纸片和负极纸片分别接入至各自集流体后进行封装。通过对封装时的预留口抽真空后，再将适量六氟磷酸锂注入，最后封闭预留口。将封装好的纸电池进行铣孔，集流体接入电路即形成可充式纸片锂电池。The graphene/active material composite positive electrode paper, the separator paper, and the carbon material composite negative electrode paper are sequentially laminated or sequentially laminated, and the positive electrode paper sheet and the negative electrode paper sheet are respectively connected to respective current collectors and then packaged. After vacuuming the reserved port at the time of packaging, an appropriate amount of lithium hexafluorophosphate is injected, and finally the reserved port is closed. The packaged paper battery is milled, and the current collector circuit forms a rechargeable lithium battery.
实施例2Example 2
一种纸电池：A paper battery:
以纳米纤维素为原料，制备纤维纸浆，再通过造纸工艺获得纤维纸并作为隔膜纸。The fiber pulp is prepared by using nanocellulose as a raw material, and the fiber paper is obtained by a papermaking process and used as a separator paper.
将生物质石墨烯、碳纳米管和磷酸亚铁锂，按照2：1：7的比例分散在乙醇中，并加入0.5％于以上混合物质量的高分子分散剂-聚乙烯吡咯烷酮，使溶液中固含量达到10％且无沉降现象发生，随后经过充分搅拌和干燥，碳材料可将磷酸亚铁锂颗粒均匀包覆。将干燥好的复合正极材料与纤维纸浆、聚乙烯醇按照4：5：1进行混合并造纸，获得石墨烯/活性材料复合正极纸。 The biomass graphene, the carbon nanotubes and the lithium iron phosphate are dispersed in ethanol in a ratio of 2:1:7, and 0.5% of the polymer dispersant-polyvinylpyrrolidone of the above mixture mass is added to make the solution solid. The content reaches 10% and no sedimentation occurs, and after sufficient agitation and drying, the carbon material can uniformly coat the lithium iron phosphate particles. The dried composite positive electrode material was mixed with fiber pulp and polyvinyl alcohol at 4:5:1 and paper-making to obtain a graphene/active material composite positive electrode paper.
将生物质石墨烯、碳纳米管、纤维纸浆、聚乙烯醇按照2：8：75：15的比例混合并造纸，获得碳材料复合负极纸。Biomass graphene, carbon nanotubes, fiber pulp, and polyvinyl alcohol were mixed and paper-made in a ratio of 2:8:75:15 to obtain a carbon material composite negative electrode paper.
按照石墨烯/活性材料复合正极纸，隔膜纸，碳材料复合负极纸的顺序依次层叠或依次反复层叠，正极纸片和负极纸片分别接入至各自集流体后进行封装。通过对封装时的预留口抽真空后，再将适量六氟磷酸锂注入，最后封闭预留口。将封装好的纸电池进行铣孔，集流体接入电路即形成可充式纸片锂电池。The graphene/active material composite positive electrode paper, the separator paper, and the carbon material composite negative electrode paper are sequentially laminated or sequentially laminated, and the positive electrode paper sheet and the negative electrode paper sheet are respectively connected to respective current collectors and then packaged. After vacuuming the reserved port at the time of packaging, an appropriate amount of lithium hexafluorophosphate is injected, and finally the reserved port is closed. The packaged paper battery is milled, and the current collector circuit forms a rechargeable lithium battery.
实施例3Example 3
一种纸电池：A paper battery:
以纳米纤维素为原料，制备纤维纸浆，再通过造纸工艺获得纤维纸并作为隔膜纸。The fiber pulp is prepared by using nanocellulose as a raw material, and the fiber paper is obtained by a papermaking process and used as a separator paper.
将生物质石墨烯、碳纳米管和磷酸亚铁锂，按照2：1：7的比例分散在乙醇中，并加入0.5％于以上混合物质量的高分子分散剂-聚乙烯吡咯烷酮，使溶液中固含量达到10％且无沉降现象发生，随后经过充分搅拌和干燥，碳材料可将磷酸亚铁锂颗粒均匀包覆。将干燥好的复合正极材料与纤维纸浆、聚乙烯醇按照4：5：1进行混合并造纸，获得石墨烯/活性材料复合正极纸。The biomass graphene, the carbon nanotubes and the lithium iron phosphate are dispersed in ethanol in a ratio of 2:1:7, and 0.5% of the polymer dispersant-polyvinylpyrrolidone of the above mixture mass is added to make the solution solid. The content reaches 10% and no sedimentation occurs, and after sufficient agitation and drying, the carbon material can uniformly coat the lithium iron phosphate particles. The dried composite positive electrode material was mixed with fiber pulp and polyvinyl alcohol at 4:5:1 and paper-making to obtain a graphene/active material composite positive electrode paper.
将生物质石墨烯、碳纳米管、纤维纸浆、聚乙烯醇按照2：3：4：1的比例混合并造纸，获得碳材料复合负极纸。The biomass graphene, the carbon nanotubes, the fiber pulp, and the polyvinyl alcohol were mixed and paper-made in a ratio of 2:3:4:1 to obtain a carbon material composite negative electrode paper.
按照石墨烯/活性材料复合正极纸，隔膜纸，碳材料复合负极纸的顺序依次层叠或依次反复层叠，正极纸片和负极纸片分别接入至各自集流体后进行封装。通过对封装时的预留口抽真空后，再将适量六氟磷酸锂注入，最后封闭预留口。将封装好的纸电池进行铣孔，集流体接入电路即形成可充式纸片锂电池。The graphene/active material composite positive electrode paper, the separator paper, and the carbon material composite negative electrode paper are sequentially laminated or sequentially laminated, and the positive electrode paper sheet and the negative electrode paper sheet are respectively connected to respective current collectors and then packaged. After vacuuming the reserved port at the time of packaging, an appropriate amount of lithium hexafluorophosphate is injected, and finally the reserved port is closed. The packaged paper battery is milled, and the current collector circuit forms a rechargeable lithium battery.
实施例4Example 4
一种纸电池：A paper battery:
以纳米纤维素为原料，制备纤维纸浆，再通过造纸工艺获得纤维纸并作为隔膜纸。The fiber pulp is prepared by using nanocellulose as a raw material, and the fiber paper is obtained by a papermaking process and used as a separator paper.
将生物质石墨烯、碳纤维和磷酸亚铁锂，按照2：1：7的比例分散在乙醇中，并加入0.5％于以上混合物质量的高分子分散剂-聚乙烯吡咯烷酮，使溶液中固含量达到10％且无沉降现象发生，随后经过充分搅拌和干燥，碳材料可将磷酸亚铁锂颗粒均匀包覆。将干燥好的复合正极材料与纤维纸浆、聚乙烯醇按照4：5：1进行混合并造纸，获得石墨烯/活性材料复合正极纸。The biomass graphene, carbon fiber and lithium iron phosphate are dispersed in ethanol at a ratio of 2:1:7, and 0.5% of the polymer dispersant-polyvinylpyrrolidone of the above mixture mass is added to achieve a solid content in the solution. 10% and no sedimentation occurred, followed by sufficient agitation and drying, the carbon material can uniformly coat the lithium iron phosphate particles. The dried composite positive electrode material was mixed with fiber pulp and polyvinyl alcohol at 4:5:1 and paper-making to obtain a graphene/active material composite positive electrode paper.
将生物质石墨烯、碳纤维、纤维纸浆、聚乙烯醇按照1：3：5：1的比例混合并造纸，获得碳材料复合负极纸。The biomass graphene, the carbon fiber, the fiber pulp, and the polyvinyl alcohol were mixed and ground in a ratio of 1:3:5:1 to obtain a carbon material composite negative electrode paper.
按照石墨烯/活性材料复合正极纸，隔膜纸，碳材料复合负极纸的顺序依次层叠或依次反复层叠，正极纸片和负极纸片分别接入至各自集流体后进行封装。通过对封装时的预留 口抽真空后，再将适量六氟磷酸锂注入，最后封闭预留口。将封装好的纸电池进行铣孔，集流体接入电路即形成可充式纸片锂电池。The graphene/active material composite positive electrode paper, the separator paper, and the carbon material composite negative electrode paper are sequentially laminated or sequentially laminated, and the positive electrode paper sheet and the negative electrode paper sheet are respectively connected to respective current collectors and then packaged. Through the reservation of the package After the vacuum is applied to the mouth, an appropriate amount of lithium hexafluorophosphate is injected, and finally the reserved port is closed. The packaged paper battery is milled, and the current collector circuit forms a rechargeable lithium battery.
实施例5Example 5
一种纸电池：A paper battery:
以纳米纤维素为原料，制备纤维纸浆，再通过造纸工艺获得纤维纸并作为隔膜纸。The fiber pulp is prepared by using nanocellulose as a raw material, and the fiber paper is obtained by a papermaking process and used as a separator paper.
将生物质石墨烯、碳纤维和镍钴锰三元材料,按照3：1：6的比例分散在乙醇中，并加入0.5％于以上混合物质量的高分子分散剂-聚乙烯吡咯烷酮，使溶液中固含量达到10％且无沉降现象发生，随后经过充分搅拌和干燥，碳材料可将三元材料颗粒均匀包覆。将干燥好的复合正极材料与纤维纸浆、聚乙烯醇按照3：6：1进行混合并造纸，获得石墨烯/活性材料复合正极纸。The biomass graphene, carbon fiber and nickel-cobalt-manganese ternary materials are dispersed in ethanol at a ratio of 3:1:6, and 0.5% of the above-mentioned mass of the polymer dispersant-polyvinylpyrrolidone is added to make the solution solid. The content reaches 10% and no sedimentation occurs, and after sufficient agitation and drying, the carbon material can uniformly coat the ternary material particles. The dried composite positive electrode material was mixed with fiber pulp and polyvinyl alcohol in a ratio of 3:6:1 and paper-making to obtain a graphene/active material composite positive electrode paper.
以生物质石墨烯为原料，配以高分子分散剂溶于水中，获得固含量12％的浆料。将该浆料喷涂于石墨烯/活性材料复合正极纸片表面并干燥，获得表面碳集流层。The biomass graphene is used as a raw material, and the polymer dispersant is dissolved in water to obtain a slurry having a solid content of 12%. The slurry was sprayed on the surface of the graphene/active material composite positive electrode sheet and dried to obtain a surface carbon current collecting layer.
将生物质石墨烯、碳纤维、纤维纸浆、聚乙烯醇按照1：3：5：1的比例混合并造纸，获得碳材料复合负极纸。The biomass graphene, the carbon fiber, the fiber pulp, and the polyvinyl alcohol were mixed and ground in a ratio of 1:3:5:1 to obtain a carbon material composite negative electrode paper.
按照石墨烯/活性材料复合正极纸，隔膜纸，碳材料复合负极纸的顺序依次层叠或依次反复层叠，正极纸片集流层和负极纸片分别接入至各自集流体后进行封装。通过对封装时的预留口抽真空后，再将适量六氟磷酸锂注入，最后封闭预留口。将封装好的纸电池进行铣孔，集流体接入电路即形成可充式纸片锂电池。The graphene/active material composite positive electrode paper, the separator paper, and the carbon material composite negative electrode paper are sequentially laminated or sequentially laminated, and the positive electrode paper collecting layer and the negative electrode paper sheet are respectively connected to respective current collectors and then packaged. After vacuuming the reserved port at the time of packaging, an appropriate amount of lithium hexafluorophosphate is injected, and finally the reserved port is closed. The packaged paper battery is milled, and the current collector circuit forms a rechargeable lithium battery.
实施例6Example 6
一种纸电池：A paper battery:
以纳米纤维素为原料造纸，获得纳米纤维素纸作为隔膜纸，该隔膜纸的柔韧性和强度都非常高，并具有较高的孔隙率，适合电解液的吸附。Paper is made from nanocellulose as raw material, and nanocellulose paper is obtained as separator paper. The separator paper has high flexibility and strength, and has high porosity, which is suitable for adsorption of electrolyte.
将石墨烯与碳纤维、纳米纤维素纸浆、聚乙烯醇按照1：4：4：1的比例混合进行造纸，获得多孔碳材料导电纸结构，作为正极纸片。Graphene was mixed with carbon fiber, nanocellulose pulp, and polyvinyl alcohol in a ratio of 1:4:4:1 to obtain paper, and a porous carbon material conductive paper structure was obtained as a positive electrode paper.
按照多孔碳材料导电纸，隔膜纸，锂片的顺序依次层叠或依次反复层叠，正极纸片集流层和负极锂片分别接入至各自集流体后进行封装。通过对封装时的预留口抽真空后，再将适量六氟磷酸锂注入，最后封闭预留口。将封装好的纸电池进行铣孔，集流体接入电路即形成一次性纸片锂电池。The porous carbon material conductive paper, the separator paper, and the lithium sheet are sequentially laminated or sequentially laminated, and the positive electrode paper collecting layer and the negative electrode lithium sheet are respectively connected to respective current collectors and then packaged. After vacuuming the reserved port at the time of packaging, an appropriate amount of lithium hexafluorophosphate is injected, and finally the reserved port is closed. The packaged paper battery is milled, and the current collector circuit forms a disposable lithium battery.
实施例7Example 7
一种纸电池：A paper battery:
以纳米纤维素为原料造纸，获得纳米纤维素纸作为隔膜纸，该隔膜纸的柔韧性和强度都非常高，并具有较高的孔隙率，适合电解液的吸附。 Paper is made from nanocellulose as raw material, and nanocellulose paper is obtained as separator paper. The separator paper has high flexibility and strength, and has high porosity, which is suitable for adsorption of electrolyte.
将石墨烯与碳纤维、纳米纤维素纸浆、聚乙烯醇按照2：3：4：1的比例混合进行造纸，获得多孔碳材料导电纸结构。再将该导电纸浸渍在氯化银溶液中并随后烘干，作为正极。Graphene was mixed with carbon fiber, nanocellulose pulp, and polyvinyl alcohol in a ratio of 2:3:4:1 to obtain a porous carbon material conductive paper structure. The conductive paper was then immersed in a silver chloride solution and then dried to serve as a positive electrode.
按照含氯化银多孔碳材料导电纸，隔膜纸，镁片的顺序依次层叠或依次反复层叠，正极纸片集流层和负极镁片分别接入至各自集流体后进行封装。通过对封装时的预留口抽真空后，再将适量氯化镁溶液注入，最后封闭预留口。将封装好的纸电池进行铣孔，集流体接入电路即形成一次性纸片镁电池。The silver chloride porous carbon material conductive paper, the separator paper, and the magnesium sheet are sequentially laminated or sequentially laminated, and the positive electrode paper collecting layer and the negative electrode magnesium sheet are respectively connected to the respective current collectors and then packaged. After vacuuming the reserved port at the time of packaging, an appropriate amount of magnesium chloride solution is injected, and finally the reserved port is closed. The packaged paper battery is milled, and the current collector circuit forms a disposable paper magnesium battery.
该实施例的镁片可以用镁合金片替代，替代后对电池的性能影响不大。The magnesium sheet of this embodiment can be replaced with a magnesium alloy sheet, and the substitution has little effect on the performance of the battery.
实施例8Example 8
一种纸电池：A paper battery:
以纳米纤维素为原料，制备纤维纸浆，再通过造纸工艺获得纤维纸并作为隔膜纸。The fiber pulp is prepared by using nanocellulose as a raw material, and the fiber paper is obtained by a papermaking process and used as a separator paper.
将生物质石墨烯、碳纳米管和钴酸锂，按照2：1：7的比例分散在乙醇中并加入一定量的高分子分散剂，使溶液中固含量达到10％且无沉降现象发生，随后经过充分搅拌和干燥，碳材料可将磷酸亚铁锂颗粒均匀包覆。将干燥好的复合正极材料与纤维纸浆、改性淀粉按照4：5：1进行混合并造纸，获得石墨烯/活性材料复合正极纸。Biomass graphene, carbon nanotubes and lithium cobalt oxide are dispersed in ethanol at a ratio of 2:1:7 and a certain amount of polymer dispersant is added to make the solid content in the solution reach 10% and no sedimentation occurs. The carbon material can then uniformly coat the lithium iron phosphate particles after thorough agitation and drying. The dried composite positive electrode material is mixed with the fiber pulp and the modified starch according to 4:5:1 and paper-making to obtain a graphene/active material composite positive electrode paper.
将生物质石墨烯、碳纳米管、纤维纸浆、改性淀粉按照1：3：5：1的比例混合并造纸，获得碳材料复合负极纸。The biomass graphene, the carbon nanotubes, the fiber pulp, and the modified starch were mixed and paper-made in a ratio of 1:3:5:1 to obtain a carbon material composite negative electrode paper.
按照石墨烯/活性材料复合正极纸，隔膜纸，碳材料复合负极纸的顺序依次层叠或依次反复层叠，正极纸片和负极纸片分别接入至各自集流体后进行封装。通过对封装时的预留口抽真空后，再将适量六氟磷酸锂注入，最后封闭预留口。将封装好的纸电池进行铣孔，集流体接入电路即形成可充式纸片锂电池。The graphene/active material composite positive electrode paper, the separator paper, and the carbon material composite negative electrode paper are sequentially laminated or sequentially laminated, and the positive electrode paper sheet and the negative electrode paper sheet are respectively connected to respective current collectors and then packaged. After vacuuming the reserved port at the time of packaging, an appropriate amount of lithium hexafluorophosphate is injected, and finally the reserved port is closed. The packaged paper battery is milled, and the current collector circuit forms a rechargeable lithium battery.
实施例9Example 9
一种纸电池：A paper battery:
以纳米纤维素为原料，制备纤维纸浆，再通过造纸工艺获得纤维纸并作为隔膜纸。The fiber pulp is prepared by using nanocellulose as a raw material, and the fiber paper is obtained by a papermaking process and used as a separator paper.
将生物质石墨烯、碳纳米管和锰酸锂，按照2：1：7的比例分散在乙醇中并加入一定量的高分子分散剂，使溶液中固含量达到10％且无沉降现象发生，随后经过充分搅拌和干燥，碳材料可将磷酸亚铁锂颗粒均匀包覆。将干燥好的复合正极材料与纤维纸浆、阴离子聚丙烯酰胺按照4：5：1进行混合并造纸，获得石墨烯/活性材料复合正极纸。The biomass graphene, carbon nanotubes and lithium manganate are dispersed in ethanol at a ratio of 2:1:7 and a certain amount of polymer dispersant is added to make the solid content in the solution reach 10% and no sedimentation occurs. The carbon material can then uniformly coat the lithium iron phosphate particles after thorough agitation and drying. The dried composite positive electrode material was mixed with fiber pulp and anionic polyacrylamide at 4:5:1 and paper-making to obtain a graphene/active material composite positive electrode paper.
将生物质石墨烯、碳纳米管、纤维纸浆、阴离子聚丙烯酰胺按照1：3：5：1的比例混合并造纸，获得碳材料复合负极纸。The biomass graphene, the carbon nanotubes, the fiber pulp, and the anionic polyacrylamide were mixed at a ratio of 1:3:5:1 and paper-made to obtain a carbon material composite negative electrode paper.
按照石墨烯/活性材料复合正极纸，隔膜纸，碳材料复合负极纸的顺序依次层叠或依次反复层叠，正极纸片和负极纸片分别接入至各自集流体后进行封装。通过对封装时的预留口抽真空后，再将适量六氟磷酸锂注入，最后封闭预留口。将封装好的纸电池进行铣孔， 集流体接入电路即形成可充式纸片锂电池。The graphene/active material composite positive electrode paper, the separator paper, and the carbon material composite negative electrode paper are sequentially laminated or sequentially laminated, and the positive electrode paper sheet and the negative electrode paper sheet are respectively connected to respective current collectors and then packaged. After vacuuming the reserved port at the time of packaging, an appropriate amount of lithium hexafluorophosphate is injected, and finally the reserved port is closed. Milling the packaged paper battery, The current collector access circuit forms a rechargeable lithium battery.
实施例10Example 10
一种纸电池：A paper battery:
以纳米纤维素为原料，制备纤维纸浆，再通过造纸工艺获得纤维纸并作为隔膜纸。The fiber pulp is prepared by using nanocellulose as a raw material, and the fiber paper is obtained by a papermaking process and used as a separator paper.
将生物质石墨烯、碳纳米管和磷酸铁锂，按照2：1：7的比例分散在乙醇中并加入一定量的高分子分散剂，使溶液中固含量达到10％且无沉降现象发生，随后经过充分搅拌和干燥，碳材料可将磷酸亚铁锂颗粒均匀包覆。将干燥好的复合正极材料与纤维纸浆、羧甲基纤维素按照4：5：1进行混合并造纸，获得石墨烯/活性材料复合正极纸。The biomass graphene, carbon nanotubes and lithium iron phosphate are dispersed in ethanol at a ratio of 2:1:7 and a certain amount of polymer dispersant is added to make the solid content in the solution reach 10% and no sedimentation occurs. The carbon material can then uniformly coat the lithium iron phosphate particles after thorough agitation and drying. The dried composite positive electrode material was mixed with fiber pulp and carboxymethyl cellulose according to 4:5:1 and paper-making to obtain a graphene/active material composite positive electrode paper.
将生物质石墨烯、碳纳米管、纤维纸浆、羧甲基纤维素按照1：3：5：1的比例混合并造纸，获得碳材料复合负极纸。The biomass graphene, the carbon nanotubes, the fiber pulp, and the carboxymethyl cellulose were mixed at a ratio of 1:3:5:1 and paper-made to obtain a carbon material composite negative electrode paper.
按照石墨烯/活性材料复合正极纸，隔膜纸，碳材料复合负极纸的顺序依次层叠或依次反复层叠，正极纸片和负极纸片分别接入至各自集流体后进行封装。通过对封装时的预留口抽真空后，再将适量六氟磷酸锂注入，最后封闭预留口。将封装好的纸电池进行铣孔，集流体接入电路即形成可充式纸片锂电池。The graphene/active material composite positive electrode paper, the separator paper, and the carbon material composite negative electrode paper are sequentially laminated or sequentially laminated, and the positive electrode paper sheet and the negative electrode paper sheet are respectively connected to respective current collectors and then packaged. After vacuuming the reserved port at the time of packaging, an appropriate amount of lithium hexafluorophosphate is injected, and finally the reserved port is closed. The packaged paper battery is milled, and the current collector circuit forms a rechargeable lithium battery.
实施例11Example 11
一种发热型导电纸：A heat-generating conductive paper:
将生物质石墨烯、碳纳米管、纤维纸浆、聚乙烯醇按照1：3：5：1的比例混合并造纸，获得碳材料复合导电纸。使用铜浆(银浆)在导电纸表面印刷出电极和线路。则发热纸制作完毕。最后，使用绝缘层(PET等材质)对发热纸进行整体封装。The biomass graphene, the carbon nanotubes, the fiber pulp, and the polyvinyl alcohol were mixed and ground in a ratio of 1:3:5:1 to obtain a carbon material composite conductive paper. Electrodes and wires were printed on the surface of the conductive paper using copper paste (silver paste). Then the heat paper is finished. Finally, the heat-generating paper is integrally packaged using an insulating layer (material such as PET).
本实施例获得的加热纸轻便，柔韧性好，适用于小工作电压工作，工作温度适宜人体承受。可嵌入服装、人体护理可穿戴物品中，使用3.7V电压进行供电，通过调节电压输出，可使温度控制在30-60摄氏度。The heating paper obtained in this embodiment is light in weight, good in flexibility, and is suitable for working at a small working voltage, and the working temperature is suitable for the human body to bear. It can be embedded in clothing and body care wearables, and is powered by 3.7V. By adjusting the voltage output, the temperature can be controlled at 30-60 degrees Celsius.
实验experiment
考察以上实施例提供的电池的性能，并与现有技术作对比，结果如表1。The performance of the battery provided in the above examples was examined and compared with the prior art, and the results are shown in Table 1.
表1纸电池的性能Table 1 Paper battery performance
  比容量Specific capacity 500圈循环后效率Efficiency after 500 cycles
实施例1Example 1 4mAh/cm24mAh/cm2 87％87%
实施例2Example 2 3.7mAh/cm23.7mAh/cm2 89％89%
实施例3Example 3 4.1mAh/cm24.1mAh/cm2 85％85%
实施例4Example 4 4mAh/cm24mAh/cm2 85％85%
实施例5Example 5 5.5mAh/cm25.5mAh/cm2 80％80%
实施例6Example 6 38mAh/cm238mAh/cm2 一次性电池不可充Disposable battery can not be charged
实施例7Example 7 42mAh/cm242mAh/cm2 一次性电池不可充Disposable battery can not be charged
实施例8Example 8 3.2mAh/cm23.2mAh/cm2 90％90%
实施例9Example 9 2.5mAh/cm22.5mAh/cm2 89％89%
实施例10Example 10 3.8mAh/cm23.8mAh/cm2 82％82%
对比1Comparison 1 2.5-5mAh/cm22.5-5mAh/cm2 一次性电池不可充Disposable battery can not be charged
对比1为：以色列Powerpaper公司纸电池专利HK20010101229，采用的电极材料分别为锌和二氧化锰，电解液为氯化锌。Comparison 1 is: Israel Powerpaper company paper battery patent HK20010101229, the electrode materials used are zinc and manganese dioxide, and the electrolyte is zinc chloride.
比容量的测试方法：采用常规蓝电电池测试系统测试充放电容量。Test method for specific capacity: The charge and discharge capacity was tested using a conventional blue battery test system.
循环效率的测试方法：采用常规蓝电电池测试系统。Test method for cycle efficiency: A conventional blue battery test system is used.
尽管已用具体实施例来说明和描述了本发明，然而应意识到，在不背离本发明的精神和范围的情况下可以作出许多其它的更改和修改。因此，这意味着在所附权利要求中包括属于本发明范围内的所有这些变化和修改。 While the invention has been illustrated and described with reference to the embodiments of the present invention, it will be understood that many modifications and changes can be made without departing from the spirit and scope of the invention. Accordingly, it is intended to embrace in the appended claims

Claims (20)

  1. 一种用于纸电极的复合材料，其特征在于，主要由碳材料、纸浆和助剂以5-10：34-57：6-9的质量比制成；所述碳材料至少包含有石墨烯，所述助剂为选自改性淀粉、阴离子聚丙烯酰胺、聚乙烯醇和羧甲基纤维素组成的组中的一种或多种。A composite material for paper electrodes, characterized in that it is mainly made of a carbon material, a pulp and an auxiliary agent in a mass ratio of 5-10:34-57:6-9; the carbon material contains at least graphene The auxiliary agent is one or more selected from the group consisting of modified starch, anionic polyacrylamide, polyvinyl alcohol, and carboxymethyl cellulose.
  2. 根据权利要求1所述的复合材料，其特征在于，所述碳材料还至少包含碳纤维和碳纳米管中的一种；所述碳材料中石墨烯的含量优选为65wt％-75wt％。The composite material according to claim 1, wherein the carbon material further comprises at least one of carbon fibers and carbon nanotubes; and the content of graphene in the carbon material is preferably from 65 wt% to 75 wt%.
  3. 一种纸电极，其特征在于，主要由正极活性材料和权利要求1或2所述的复合材料制成，且两者的质量百分比分别为30-50％，50-70％。A paper electrode characterized by being mainly composed of a positive electrode active material and the composite material according to claim 1 or 2, and the mass percentages of the two are 30-50%, 50-70%, respectively.
  4. 根据权利要求3所述的纸电极，其特征在于，所述正极活性材料为选自由锰酸锂、钴酸锂、磷酸铁锂、磷酸亚铁锂和三元镍钴锰组成的组中的一种或多种。The paper electrode according to claim 3, wherein the positive electrode active material is one selected from the group consisting of lithium manganate, lithium cobaltate, lithium iron phosphate, lithium iron phosphate, and ternary nickel cobalt manganese. Kind or more.
  5. 根据权利要求3或4所述的纸电极，其特征在于，所述碳材料、所述纸浆、所述助剂和所述正极活性材料的质量百分比分别为：5-10％，34-57％，6-9％，30-50％。The paper electrode according to claim 3 or 4, wherein the carbon material, the pulp, the auxiliary agent and the positive electrode active material have mass percentages of 5-10%, 34-57%, respectively. , 6-9%, 30-50%.
  6. 根据权利要求3所述的纸电极，其特征在于，还包括分散剂；所述分散剂优选为聚乙烯吡咯烷酮。A paper electrode according to claim 3, further comprising a dispersing agent; and said dispersing agent is preferably polyvinylpyrrolidone.
  7. 一种纸电池，其特征在于，包括主要由权利要求3-6任一项所述的纸电极组成的正极纸。A paper battery comprising a positive electrode paper mainly composed of the paper electrode according to any one of claims 3-6.
  8. 根据权利要求7所述的纸电池，其特征在于，还包括负极纸，所述负极纸主要由所述碳材料、所述纸浆和所述助剂以10-50％：40-75％：8-18％的质量百分比制成。A paper cell according to claim 7, further comprising a negative paper mainly composed of said carbon material, said pulp and said auxiliary agent at 10-50%: 40-75%: 8 Made of -18% by mass.
  9. 根据权利要求7所述的纸电池，其特征在于，还包括隔膜纸和电解液，所述石墨烯纸电池由所述正极纸、所述隔膜纸和所述负极纸依次叠压而成，并且所述正极纸、所述隔膜纸和所述负极纸浸渍于所述电解液中并封装。The paper battery according to claim 7, further comprising a separator paper and an electrolytic solution, wherein the graphene paper battery is formed by sequentially laminating the positive electrode paper, the separator paper, and the negative electrode paper, and The positive paper, the separator paper, and the negative paper are immersed in the electrolytic solution and encapsulated.
  10. 根据权利要求9所述的纸电池，其特征在于，所述电解液为选自六氟磷酸锂、高氯酸锂和四氟硼酸锂组成的组中的一种或多种。The paper battery according to claim 9, wherein the electrolyte is one or more selected from the group consisting of lithium hexafluorophosphate, lithium perchlorate, and lithium tetrafluoroborate.
  11. 一种石墨烯导电纸，其特征在于，主要由碳材料、纸浆和助剂以10-50％、40-75％、8-18％的质量百分比制成；所述碳材料至少包含有石墨烯，所述助剂为选自由改性淀粉、阴离子聚丙烯酰胺、聚乙烯醇和羧甲基纤维素组成的组中的一种或多种。A graphene conductive paper characterized in that it is mainly made of carbon materials, pulp and auxiliary materials in a mass percentage of 10-50%, 40-75%, 8-18%; the carbon material contains at least graphene The auxiliary agent is one or more selected from the group consisting of modified starch, anionic polyacrylamide, polyvinyl alcohol, and carboxymethyl cellulose.
  12. 根据权利要求11所述的石墨烯导电纸，其特征在于，所述碳材料还至少包含碳纤维和碳纳米管中的一种；所述纸浆优选为纳米纤维纸浆。The graphene conductive paper according to claim 11, wherein the carbon material further comprises at least one of carbon fibers and carbon nanotubes; and the pulp is preferably nanofiber pulp.
  13. 根据权利要求11或12所述的石墨烯导电纸，其特征在于，所述碳材料中石墨烯的含量为20wt％-40wt％。The graphene conductive paper according to claim 11 or 12, wherein the carbon material has a graphene content of 20% by weight to 40% by weight.
  14. 根据权利要求11所述的石墨烯导电纸，其特征在于，所述碳材料、所述 纸浆和所述助剂的质量百分比分别为：10-40％、50-75％、10-15％。The graphene conductive paper according to claim 11, wherein said carbon material, said said The mass percentages of the pulp and the auxiliary agent are: 10-40%, 50-75%, 10-15%, respectively.
  15. 根据权利要求11所述的石墨烯导电纸，其特征在于，所述碳材料、所述纸浆和所述助剂的质量百分比分别为：30-50％、40-56％、10-14％。The graphene conductive paper according to claim 11, wherein the carbon material, the pulp and the auxiliary agent have mass percentages of 30-50%, 40-56%, and 10-14%, respectively.
  16. 一种石墨烯纸电池，其特征在于，所述石墨烯纸电池的正极纸或负极纸中的一个主要由权利要求11-15任一项所述的石墨烯导电纸制成。A graphene paper battery characterized in that one of a positive electrode paper or a negative electrode paper of the graphene paper battery is mainly made of the graphene conductive paper according to any one of claims 11 to 15.
  17. 根据权利要求16所述的石墨烯纸电池，其特征在于，所述正极纸主要由所述石墨烯导电纸制成，所述负极纸为电势低于正极纸的金属箔片或涂覆于基体的金属涂层；所述金属箔片或所述金属涂层优选为金属锂或镁。The graphene paper cell according to claim 16, wherein the positive electrode paper is mainly made of the graphene conductive paper, and the negative electrode paper is a metal foil having a potential lower than that of the positive electrode paper or coated on the substrate. Metal coating; the metal foil or the metal coating is preferably metallic lithium or magnesium.
  18. 根据权利要求16所述的石墨烯纸电池，其特征在于，所述正、负极纸主要由所述石墨烯导电纸制成，且所述正极纸至少含有正极活性材料；所述正极活性材料优选为选自由锰酸锂、钴酸锂、磷酸铁锂、磷酸亚铁锂和三元镍钴锰组成的组中的一种或多种。The graphene paper cell according to claim 16, wherein the positive and negative papers are mainly made of the graphene conductive paper, and the positive electrode paper contains at least a positive electrode active material; It is one or more selected from the group consisting of lithium manganate, lithium cobaltate, lithium iron phosphate, lithium iron phosphate, and ternary nickel cobalt manganese.
  19. 根据权利要求16-18任一项所述的石墨烯纸电池，其特征在于，所述石墨烯纸电池由所述正极纸、隔膜纸和所述负极纸依次叠压而成，并且所述正极纸、所述隔膜纸和所述负极纸浸渍于电解液中并封装。The graphene paper cell according to any one of claims 16 to 18, wherein the graphene paper battery is formed by sequentially laminating the positive electrode paper, the separator paper, and the negative electrode paper, and the positive electrode The paper, the separator paper, and the negative paper are immersed in an electrolyte and packaged.
  20. 根据权利要求11-15任一项所述的石墨烯导电纸的应用，其特征在于，所述石墨烯导电纸用于制作可穿戴器件或服饰的电源，或者用于制作导电面膜的电源。 Use of the graphene conductive paper according to any one of claims 11 to 15, characterized in that the graphene conductive paper is used for producing a power source for a wearable device or apparel, or a power source for making a conductive mask.
PCT/CN2017/079335 2016-04-01 2017-04-01 Composite material for paper electrode, paper electrode, conductive graphene sheet, paper battery, and application thereof WO2017167312A1 (en)

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