CN108172760A - A kind of paper combination electrode and preparation method thereof - Google Patents
A kind of paper combination electrode and preparation method thereof Download PDFInfo
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- CN108172760A CN108172760A CN201711424162.8A CN201711424162A CN108172760A CN 108172760 A CN108172760 A CN 108172760A CN 201711424162 A CN201711424162 A CN 201711424162A CN 108172760 A CN108172760 A CN 108172760A
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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
- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
-
- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
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- 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
Abstract
The invention discloses a kind of paper combination electrode and preparation method thereof, including：It using paper grade pulp as matrix, is mixed by Mechanical Method with carbon nanomaterial and active electrode material of lithium ion battery, is manufactured paper with pulp paper with the slurry being mixed into；Electrode plates are made in the paper roll-in of acquisition；The raw material that paper method for preparing composite electrode provided by the invention uses is easy to get, inexpensively, preparation process it is simple, the production cost of flexible two-dimensional electrode can be substantially reduced, produced conducive to amplification；There is the paper combination electrode that preparation method of the present invention obtains a kind of ternary mutually to entwine structure, it is integrated with the flexible, porous structure of wood-fibred, the conductive network framework of conductive carbon material and active electrode material of lithium ion battery, with excellent charging and discharging capacity and cyclical stability, flexible two-dimensional shapes, plasticity are high.
Description
Technical field
The present invention relates to lithium ion battery preparing technical field, specifically a kind of paper combination electrode, and the present invention
Additionally provide the preparation method of the paper combination electrode.
Background technology
In recent years, with the rapid development of electronic technology, electronic equipment is towards lightening, flexibility and wearable
Direction is developed, such as the companies such as Samsung and LG are all proposed curved surface screen mobile phone, and foldable, flexible new to developing
Generation product develops.One of challenge of development flexible electronic device maximum is exactly light thin and flexible electricity adaptable therewith at present
Chemical energy storage device, the products such as traditional lithium ion battery, ultracapacitor be it is unyielding, bending, fold when, easily
Electrode material and collector is caused to detach, influences chemical property, shortens the service life, Shenzhen leads to short circuit, serious safety occurs
Problem, therefore for the development for adapting to next-generation flexible electronic devices, the development work of flexible energy storage device is extremely urgent.
Lithium ion battery energy density is high, has good stable circulation performance, is that the flexible energy storage equipment of development is more managed
The energy storage device thought, at present, three problems that flexible lithium ion battery faces：1) design and preparation of flexible electrode；2) it is bent
The stability of device chemical property in folding process；3) high-performance density and high power density.
In view of this, it is special to propose the present invention.
Invention content
The technical problem to be solved in the present invention is to overcome the deficiencies of the prior art and provide a kind of paper combination electrode, to make
Paper paper pulp, carbon nanomaterial, lithium ion battery active material prepare ternary three-dimensional paper combination electrode for raw material, with ternary phase
Mutual entwine structure and good charging and discharging capacity and cyclical stability；The present invention also provides the preparation method of the electrode, tools
There is the features such as cost of raw material is low in cost and easily available, preparation process is simple.
In order to solve the above technical problems, the present invention is using the basic conception of technical solution：
A kind of preparation method of paper combination electrode, including
Using paper grade pulp as matrix, carried out with carbon nanomaterial and active electrode material of lithium ion battery by Mechanical Method
Mixing is manufactured paper with pulp paper with the slurry being mixed into；
Paper material roll-in will be obtained, electrode plates are made.
Further, in the preparation method of above-mentioned paper combination electrode：Lithium ion battery is lived in the composite construction paper
Property electrode material weight percentage be 50%-90%；The weight percentage of carbon nanomaterial is 5%-45%；Paper substrate wood
The weight percentage of fiber is not more than 5%；Each material forms structure of mutually entwining, the knot of mutually entwining in composite construction paper
Structure refers to the composite construction that three kinds of materials are permeated, mixed each other.
Further, in the preparation method of above-mentioned paper combination electrode：The carbon nanomaterial includes：Carbon nanotube, stone
It is arbitrary in black alkene, graphene oxide, the graphene oxide of reduction, carbon fiber and bacteria cellulose based carbon fiber/cilium
One or more kinds of combinations.
Further, in the preparation method of above-mentioned paper combination electrode：The active electrode material of lithium ion battery includes：
The metal that alloying reaction can occur with lithium, with lithium conversion reaction can occur for the carbon that intercalation compound can be formed with lithium
Transistion metal compound and embedding lithium type transition metal oxide in one or more kinds of combinations.
Further, in the preparation method of above-mentioned paper combination electrode：The carbon that intercalation compound can be formed with lithium
Including：Electrographite, native graphite, carbonaceous mesophase spherules, petroleum coke, carbon fiber, thermal decomposed resins carbon；Alloy can occur with lithium
The metal for changing reaction includes：Tin, silicon, germanium, aluminium, magnesium, alloy；The transistion metal compound packet of conversion reaction can occur with lithium
It includes：Iron oxide, titanium oxide, zinc oxide；Embedding lithium type transition metal oxide includes lithium titanate, LiMn2O4, cobalt acid lithium and ferric phosphate
Lithium.
Further, in the preparation method of above-mentioned paper combination electrode：It is described manufacture paper with pulp paper the step of include：It will be described mixed
Approach flow, dehydration, molding, squeezing and the drying of synthesis.
The present invention also provides a kind of paper combination electrode obtained by above-mentioned preparation method, electrode is lived by lithium ion battery
Property electrode material and carbon nanomaterial and wood-fibred composition；The wherein weight percentage of active electrode material of lithium ion battery
For 50%-90%；The weight percentage of carbon nanomaterial is 5%-45%；The weight percentage of wood-fibred is not more than 5%；
The electrode be two-dimension flexible electrode, thickness 0.05-5cm.
Also, the present invention gives a kind of above-mentioned paper combination electrode and is used as support electrode in lithium rechargeable battery
Application.
The present invention also provides a kind of electrochemical energy storing device, included in the electrochemical energy storing device by above-mentioned preparation side
The paper combination electrode that method obtains.
After adopting the above technical scheme, the present invention has the advantages that compared with prior art：
The raw material that paper method for preparing composite electrode provided by the invention uses is easy to get, inexpensively, preparation process is simple and consumes energy
It is low, the production cost of flexible two-dimensional electrode can be substantially reduced, is produced conducive to amplification；The paper compound electric that preparation method of the present invention obtains
Have ternary mutually to entwine structure, be integrated with the flexible, porous structure of wood-fibred, the conductive network framework of conductive carbon material with
And active electrode material of lithium ion battery, there is excellent charging and discharging capacity and cyclical stability, flexible two-dimensional shapes are plastic
Property it is high；The present invention also provides above-mentioned paper combination electrode as support electrode secondary lithium battery application and comprising
The electrochemical energy storing device (such as secondary lithium battery) of the paper combination electrode.
Specific embodiment
With reference to specific embodiment, the invention will be further described, to help present disclosure is understood.
A kind of preparation method of paper combination electrode provided by the invention, including：
Using water or organic solvent as solvent, using industrial paper making pulp as matrix, with carbon nanomaterial and lithium ion battery
Active electrode material is mixed by Mechanical Method；
It is manufactured paper with pulp paper with the slurry being mixed into：By the approach flow being mixed into, dehydration, molding, squeezing and drying
To prepare composite construction paper；The weight percent of active electrode material of lithium ion battery in the composite construction paper obtained
Content is 50%-90%；The weight percentage of carbon nanomaterial is 5%-45%；The weight percentage of paper substrate wood-fibred is not
More than 5%.Each material composition is mutually entwined structure in composite construction paper, that is, three kinds of materials permeate each other, it is compound to mix
Structure.
Then electrode plates are made in the paper composite construction paper roll-in of acquisition.
In the preparation method, the carbon nanomaterial includes：Carbon nanotube, graphene, graphene oxide, reduction
Any one in graphene oxide, carbon fiber and bacteria cellulose based carbon fiber/cilium or two or more combinations.
The active electrode material of lithium ion battery includes one or more kinds of combinations in following different materials：
The carbon of intercalation compound can be formed with lithium, such as electrographite, native graphite, carbonaceous mesophase spherules, petroleum coke, carbon
Fiber, thermal decomposed resins carbon；
Can with lithium occur alloying reaction metal, as tin, silicon, germanium, aluminium, magnesium and other can with lithium occur alloying
The alloy of reaction；
The transistion metal compound of conversion reaction can occur with lithium, such as iron oxide, titanium oxide, zinc oxide；
And in embedding lithium type transition metal oxide, such as lithium titanate, LiMn2O4, cobalt acid lithium and LiFePO4.
By paper making pulp to manufacture paper with pulp after matrix, with carbon nanomaterial and active electrode material of lithium ion battery mechanical mixture
Paper, can directly acquire ternary three-dimensional paper composites, and ternary three-dimensional paper composites are the flexible, porous for being integrated with wood-fibred
The paper sandwich of structure, the conductive network framework of conductive carbon material and active electrode material of lithium ion battery, the paper
Three kinds of materials permeate, entwine each other in composite structure, and component integration is high, in long-term charge and discharge and deformation process, drops significantly
The loss of low active component and capacitance loss happen.
With the paper composites (composite construction paper) of acquisition, can further by being heat-treated under non-oxidizing atmosphere,
Make the wood-fibred in paper composites that carbonization occur and/or be denaturalized, electrode plates are made in the paper composites roll-in obtained later.
Wherein non-oxidizing atmosphere is provided by following at least one gas：Nitrogen, argon gas, hydrogen, helium and titanium dioxide
Carbon；Preferably, heat treatment temperature is 100-500 DEG C.
For above-mentioned preparation method, the present invention provides following embodiment and is further described.
Embodiment 1
The paper making pulp of appropriate concentration and carbon nanotube and nano silicon particles are subjected to mechanical mixture, utilize mixed slurry
Material is manufactured paper with pulp paper, to obtain ternary three-dimensional paper sandwich, lithium ion battery active electrode in the paper sandwich
The weight percentage of material nano silicon particles is 90%, and the weight percentage of carbon nanotube is 5%, the percentage of lignose
Content is 5%.
Cathode pole piece is made in paper composites roll-in obtained, using cathode pole piece as test electrode, using metallic lithium foil as
To electrode, electrolyte is 1M LiPF6/EC:DEC(1:1；V/v), i.e., the ethylene carbonate and carbonic acid dissolved with lithium hexafluoro phosphate
The mixed solvent of diethylester, diaphragm are Celgard 2400, and knob is assembled into the glove box for being respectively less than 1ppm in oxygen and water content
Fastening lithium ionic cell.
By examining, under the current density of 0.5C, which has the volume and capacity ratio of up to 1551mAh/cm3；
After being recycled 90 times under the current density of 1C, capacity retention ratio is up to 97%.
Embodiment 2
The paper making pulp of appropriate concentration and graphene and ferric oxide nanometer particle are subjected to mechanical mixture, utilization is mixed
Slurry is manufactured paper with pulp paper, and to obtain ternary three-dimensional paper sandwich, electrode plates are made in gained paper composite wood roll-in, which answers
The weight percentage of active electrode material of lithium ion battery ferric oxide nanometer particle is 50% in composite electrode, the weight of graphene
Percentage composition is 45%, and the percentage composition of lignose is 5%.
By follow-up test such as embodiment 1.Under the current density of 0.5C, there is the volume specific volume of up to 960mAh/cm3
Amount；After being recycled 70 times under the current density of 1C, capacity retention ratio is up to 95%.
Embodiment 3
The paper making pulp of appropriate concentration and graphene oxide and nano silicon particles are subjected to mechanical mixture, utilize the mixing
Slurry is manufactured paper with pulp paper, and paper composite electrode pole piece is made in 500 DEG C of processing, roll-in to gained paper composites in a hydrogen atmosphere.Gained
The weight percentage of active electrode material of lithium ion battery ferric oxide nanometer particle is 60% in paper combination electrode, graphene
Weight percentage is 25%, and the percentage composition of lignose is 15%.
Follow-up test such as embodiment 1.Under the current density of 0.5C, there is the volume specific volume of up to 1325mAh/cm3
Amount；After being recycled 45 times under the current density of 1C, capacity retention ratio is up to 97%.
Embodiment 4
The paper making pulp of appropriate concentration and carbon nanotube and tin oxide nanoparticles are subjected to mechanical mixture, mixed using described
It closes slurry to manufacture paper with pulp paper, paper composite electrode pole piece is made in gained paper composites roll-in, and lithium ion battery is lived in paper combination electrode
Property electrode material tin oxide nanoparticles weight percentage for 75%, the weight percentage of carbon nanotube is 15%, wood
The percentage composition of cellulose is 10%.
Follow-up test such as embodiment 1.Under the current density of 0.5C, there is the volume specific volume of up to 735mAh/cm3
Amount；After being recycled 70 times under the current density of 1C, capacity retention ratio is up to 94%.
Embodiment 5
The paper making pulp of appropriate concentration and graphene and lithium titanate nano particle are subjected to mechanical mixture, utilize the mixing
Slurry is manufactured paper with pulp paper, and gained paper composites roll-in is made paper composite electrode pole piece, lithium ion battery activity in paper combination electrode
The weight percentage of electrode material lithium titanate nano particle is 60%, and the weight percentage of graphene is 35%, wood-fibred
The percentage composition of element is 5%.
Follow-up test such as embodiment 1.Under the current density of 0.5C, there is the volume specific volume of up to 650mAh/cm3
Amount；After being recycled 150 times under the current density of 1C, capacity retention ratio is up to 98%.
Embodiment 6
The paper making pulp of appropriate concentration and carbon nanotube and natural graphite particles are subjected to mechanical mixture, utilize the mixing
Slurry is manufactured paper with pulp paper, and the weight percentage of active electrode material of lithium ion battery graphite particle is in gained paper composites
80%, the weight percentage of carbon nanotube is 15%, and the percentage composition of lignose is 5%；Making appropriate concentration simultaneously
Paper paper pulp and graphene and cobalt acid lithium particle carry out mechanical mixture, are manufactured paper with pulp paper using the mixed slurry, gained paper composite wood
The weight percentage of active electrode material of lithium ion battery cobalt acid lithium particle is 80% in material, the weight percentage of graphene
It is 10%, the percentage composition of lignose is 10%.
By two paper sandwich obtained, anode and cathode pole piece is made in roll-in respectively, with 1M LiPF6/EC:DEC
(1:1；V/v) it is electrolyte, the i.e. mixed solvent of the ethylene carbonate dissolved with lithium hexafluoro phosphate and diethyl carbonate,
Celgard 2400 is diaphragm, and button-shaped lithium ion battery is assembled into the glove box for being respectively less than 1ppm in oxygen and water content.It will
Test, the lithium ion battery have the volume and capacity ratio of up to 688mAh/cm3 under the current density of 0.5C；In the electricity of 1C
After being recycled 100 times under current density, capacity retention ratio is up to 95%.
The present invention is used as lithium ion cell electrode by two-dimension flexible paper electrode prepared by the preparation method of paper combination electrode
During material, a. is integrated with the advantage of the framework of the characteristic of wood fibre itself and conductive carbon material conductive network in paper pulp, paper
The characteristic of wood fibre itself, that is, flexible, porous structure in slurry：Be conducive to the transmission of lithium ion and conducive to electrode material volume
The release of stress caused by variation, the expansion of effective accommodate electrod material volume, so as to ensure that nano material self structure
Integrality avoids destruction of the volume expansion to external electrode structure；The framework of conductive carbon material conductive network is conducive to electronics
With the transmission of lithium ion, high rate performance is improved；B. reduce the use of collector in conventional electrode configurations, be conducive to improve battery
Whole volume and capacity ratio and energy density per unit volume, so as to the micromation of convenient battery；C. plasticity is high, and paper combination electrode is flexibility
Two-dimensional structure can construct the battery structure of arbitrary shape；The paper combination electrode that this method obtains is as lithium ion cell electrode material
Material shows extremely excellent charging and discharging capacity and cyclical stability.
Although there are some electrodes that also there is flexibility in currently available technology：Such as " paper electrode ", with carbon paper, carbon nanotube
(CNT) paper, graphene paper etc. are collector carrying active substance, and as lithium ion cell electrode, preparation method includes simple
Rubbing method, vacuum filtration method, CVD, Situ Hydrothermal deposition etc.；Such as " textile electrode ", i.e., born by collector of carbon fibre fabric
Active material is carried, prepares flexible electrode.However, this kind of active material is deposited on binary combination electrode on collector not only curved
Active material easily comes off, the electrical contact of active material and collector is easily failed, and prepares such material at present when song, folding
The equal cost of method is higher used by material, complex process is not suitable for large batch of industrialized production, restrict performance performance and
Practical application.
And in preparation method of the present invention, ternary paper composite electrode active material, carbon nanomaterial and the wood-fibred of preparation
Between be a kind of structure of mutually entwining, three kinds of materials permeate, entwine each other in the paper composite construction, and integration is high, the electrode material
Carbon nanotube forms efficient conductive network framework in material, further improves the performance of electrode material.Paper substrate and carbon nanometer material
Material also substantially increases the mechanical performances such as bending, the folding of paper combination electrode, avoids point of electrode active material and collector
From；In addition, the raw material of the combination electrode is cheap, is easy to get, preparation process is simple, energy consumption is low, can substantially reduce flexible two dimension electricity
The production cost of pole has good production can amplification.
On the other hand, the present invention provides the paper combination electrode prepared by above-mentioned preparation method, paper combination electrode by lithium from
Wood-fibred composition in sub- battery-active electrode material and carbon nanomaterial and paper pulp；Wherein lithium ion battery active electrode material
The weight percentage of material is 50%-90%；The weight percentage of carbon nanomaterial is 5%-45%；The weight hundred of wood-fibred
Content is divided to be no more than 5%；The paper combination electrode be two-dimension flexible electrode, thickness 0.05-5cm.
Wherein, the carbon nanomaterial includes：Carbon nanotube, graphene, graphene oxide, the graphene oxidation restored
Any one in object, carbon fiber and bacteria cellulose based carbon fiber/cilium or two or more combinations.
The active electrode material of lithium ion battery includes one or more kinds of combinations in following different materials：
The carbon of intercalation compound can be formed with lithium, such as electrographite, native graphite, carbonaceous mesophase spherules, petroleum coke, carbon
Fiber, thermal decomposed resins carbon；
Can with lithium occur alloying reaction metal, as tin, silicon, germanium, aluminium, magnesium and other can with lithium occur alloying
The alloy of reaction；
The transistion metal compound of conversion reaction can occur with lithium, such as iron oxide, titanium oxide, zinc oxide；
And in embedding lithium type transition metal oxide, such as lithium titanate, LiMn2O4, cobalt acid lithium and LiFePO4.
Paper combination electrode of the present invention is due to the composite construction of its internal ternary three-dimensional, as lithium ion battery electrode material
When, by test, show excellent charging and discharging capacity and cyclical stability.
So the present invention gives a kind of above-mentioned paper combination electrode and is used as support electrode in lithium rechargeable battery
Application, the self-supporting feature that the above-mentioned paper combination electrode of the present invention has in itself with its composite construction can be directly used as accumulator
The electrode of part shows high lithium storage content and cyclical stability, in the conventional lithium ion secondary cell for replacing non-paper electrode
Cathode pole piece and/or anode pole piece.
Meanwhile the present invention also provides a kind of electrochemical energy storing device, or perhaps a kind of electrochemical energy storage system, it is described
Comprising the paper combination electrode that is obtained by above-mentioned preparation method in electrochemical energy storing device or system, the electrochemical energy storing device or it is
System can be the electrochemical energy storage devices such as lithium ion battery, ultracapacitor, in bending, folding, due to paper combination electrode
Component between mutually entwine structure and flexible speciality, happening for electrode material and collector separation, pole can be avoided the occurrence of
Big degree reduces the influence even avoided to chemical property, and safe, service life is long.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of preparation method of paper combination electrode, it is characterised in that：Including
It using paper pulp as matrix, is mixed with carbon nanomaterial and active electrode material of lithium ion battery by Mechanical Method, with mixed
The slurry of synthesis is manufactured paper with pulp paper, prepares composite construction paper；
Electrode plates are made in the paper roll-in of acquisition.
2. the preparation method of paper combination electrode according to claim 1, it is characterised in that：Lithium in the composite construction paper
The weight percentage of ion battery active electrode material is 50%-90%；The weight percentage of carbon nanomaterial is 5%-
45%；The weight percentage of paper substrate wood-fibred is not more than 5%；Each material forms structure of mutually entwining in composite construction paper.
3. the preparation method of the paper combination electrode according to claim 2, it is characterised in that：The carbon nanomaterial includes：
Carbon nanotube, graphene, graphene oxide, graphene oxide, carbon fiber and the bacteria cellulose based carbon fiber/fibre restored
Any one in hair or two or more combinations.
4. the preparation method of paper combination electrode according to claim 2, it is characterised in that：The lithium ion battery activity electricity
Pole material includes：The carbon of intercalation compound can be formed with lithium, the metal of alloying reaction can occur with lithium, can be sent out with lithium
One or more kinds of combinations in the transistion metal compound and embedding lithium type transition metal oxide of raw conversion reaction.
5. the preparation method of paper combination electrode according to claim 4, it is characterised in that：It is described to form intercalation with lithium
The carbon of compound includes：Electrographite, native graphite, carbonaceous mesophase spherules, petroleum coke, carbon fiber, thermal decomposed resins carbon；It can be with
The metal that alloying reaction occurs for lithium includes：Tin, silicon, germanium, aluminium, magnesium, alloy；The transition metal of conversion reaction can occur with lithium
Compound includes：Iron oxide, titanium oxide, zinc oxide；Embedding lithium type transition metal oxide includes lithium titanate, LiMn2O4, cobalt acid lithium
And LiFePO4.
6. a kind of paper combination electrode, it is characterised in that：The combination electrode is by active electrode material of lithium ion battery and carbon nanometer
Material and wood-fibred composition；Wherein the weight percentage of active electrode material of lithium ion battery is 50%-90%；Carbon nanometer
The weight percentage of material is 5%-45%；The weight percentage of wood-fibred is not more than 5%.
7. paper combination electrode according to claim 6, it is characterised in that：The electrode be two-dimension flexible electrode, thickness 0.05-
5cm。
8. a kind of application of the paper combination electrode as support electrode in lithium rechargeable battery described in claim 7.
9. a kind of electrochemical energy storing device, it is characterised in that：It is included in the electrochemical energy storing device any by claim 1-5
The paper combination electrode that the item preparation method obtains.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111525114A (en) * | 2020-05-09 | 2020-08-11 | 四川聚创石墨烯科技有限公司 | Method for continuously preparing current collector-free silicon-carbon negative electrode paper |
| CN112176771A (en) * | 2020-09-25 | 2021-01-05 | 柔电（武汉）科技有限公司 | Preparation method of lithium-philic carbon nanotube paper and preparation method of composite metal lithium cathode |
| CN112176772A (en) * | 2020-09-25 | 2021-01-05 | 柔电（武汉）科技有限公司 | Preparation method of lithium-philic carbon nanotube paper and preparation method of composite metal lithium cathode |
| CN113502682A (en) * | 2021-06-29 | 2021-10-15 | 华南理工大学 | Cellulose-based activated carbon fiber paper and preparation method and application thereof |
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