CN106920969A - A kind of biomass water system conductive bond system and the electrochmical power source using the system - Google Patents
A kind of biomass water system conductive bond system and the electrochmical power source using the system Download PDFInfo
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
- H01M10/34—Gastight accumulators
- H01M10/345—Gastight metal hydride accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- 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
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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
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- 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 biomass conductive bonding system and the electrochmical power source using the system, belong to electrically conducting adhesive and cell art.The conductive bond system is the conducting polymer of in-situ polymerization by soluble biomass monomer under catalytic condition.The system is characterised by：Under the conditions of water system, electrode active material directly mixes with liquid monomer, and the lotion of gained is sprayed on electrode current collecting body；Under catalytic condition, the conducting polymer that monomer is generated by home position polymerization reaction directly links together active material, and be fixed on electrode current collecting body.Meanwhile, the polymeric binder of generation is conductive, can reduce or substitute the use of conductive additive in pole piece.The present invention solves the binders for electrodes that existing electrochmical power source used and does not have electric conductivity and high cost, the organic solvent for being used is expensive and there is pollution environment, used and cream technique mixing time is long, the inferior problem of positive/negative plate preparation technology low production efficiency.
Description
Technical field
The invention belongs to electrically conducting adhesive and cell art, it is related to a kind of water system for being polymerized by biomass monomer and being formed
Conductive bond system, and the electrochmical power source of conductive adhesive is formed using the biomass monomer in situ polymerization.
Background technology
Electrochmical power source is high as a kind of energy density, the energy storage system of low cost, as long as having serviced a century for the mankind,
The lithium ion battery of current popularization is exactly one kind of electrochmical power source.Future, popularization and renewable wind-powered electricity generation energy with electric automobile
The development in source, used as its first-selected energy-storage battery, the application scale of electrochmical power source will be improved further.
One typical electrochmical power source structure is made up of positive pole, negative pole, electrolyte and barrier film.Both positive and negative polarity contains electrode
Active material, conductive agent and binding agent.Wherein, the major function of binding agent is that the powders such as electrode active material and conductive agent are glued
Knot together, and is bonded on electrode current collecting body.At present, binding agent the most commonly used in lithium ion battery is the poly- of commercial synthesis
Vinylidene (PVdF)., it is necessary to use expensive organic solvent N- hydroxymethylpyrrol alkanones during the use of the binding agent
(NMP) PVdF powder is dissolved.Then, in electrode production process, substantial amounts of nmp solvent needs to evaporate, therefore, to environment
Cause greatly to pollute and endanger the healthy of people.Although NMP has certain recovery value, technically it is difficult to grasp
Make, further increase the manufacturing cost of electrochmical power source.Further, since PVdF is a kind of synthesis macromolecular material of insulation, it is
Improve the electron conduction of electrode, it is necessary to add a certain amount of conductive agent in electrode.These non-electroactive materials exist
Mass fraction in electrode is too high, reduces the energy density of electrode plates.Therefore, chemical electric power source electrode preparation method is advanced
Update, be always urgently to need improved technical barrier.
In existing patent, there is the binding agent and new electrode slurry preparation technology that substitute PVdF.Some water
It is that binding agent attempts to solve high cost and the pollution problem of PVdF and NMP systems, such as Chinese patent application
(CN102934268A, CN104882612A, CN104293239A and CN104789160A).However, these above-mentioned binding agents
It is a kind of multi-component mixing bonding system, prepares complexity, mass fraction is above 10% in shared electrode, needs in addition
Want conductive additive to improve the electric conductivity of electrode, reduce further the energy density of electrode.Although Chinese patent application
CN10486187A and CN104752729A are referred to the concept of conductive adhesive, disclose with electron conduction binding agent
Formula, but described binding agent still includes conventional binders and conductive additive, belongs to the modified method of mixing and doping, and
The binding agent for being obtained is still required for appropriate solvent and dissolves, and cream mixing time is more long, and original lithium ion is not broken through
Technology for preparing electrode, the low problem of original electrode preparation efficiency is not resolved.Chinese patent application
CN101278423A is proposed using monomer cohesive bond active material, but the monomer material for using is poisonous or expensive material
Material, dicyandiamide solution is still mainly organic system, and these factors are all unfavorable for environmental protection and cost control.Therefore, existing electricity
Pole preparation method and its bonding system are still difficult to have water system, conduction, viscoelastic these three key elements high concurrently.
The content of the invention
In present invention aim to address current electrochmical power source pole piece preparation process, the binding agent PVdF costs for being used
It is expensive, organic solvent NMP pollution environment, it is necessary to using a large amount of conductive additives, the problems such as electrode slurry incorporation time is long, there is provided one
Plant biomass water system conductive bond system and the electrochmical power source using the system.Biomass refer to logical using big gas and water, soil etc.
The various organisms crossed photosynthesis and produce, biological material and its derivative have wide material sources, cheap, environment friendly
The characteristics of good.The present inventor is had found by unremitting effort, is handed over by catalytic process, realization using biomass monomer material
Connection polymerization, the resinous polymer for being generated has abundant carbon-carbon double bond structure, with electron transfer characteristic, while biomass list
Body is readily dissolved in water, and the conductive adhesive system for relying on biomass monomer to prepare ideally can simultaneously realize conductive, water
It is solvable, three targets of viscoplasticity high, is had broad application prospects in field of chemical power source.The purpose of the present invention be by with
What lower technical scheme was realized.
The present invention provides a kind of biomass water system conductive bond system, comprising：Biomass monomer material and catalyst, its
It is characterised by, described biomass monomer material is soluble water system.Biomass monomer material is by natural biomass processing
Into natural biomass of the present invention is common biomass, and including but not limited to stalk, wood chip, rice husk, branch, sugaring is useless
Slag, water plant etc..
Further, described biomass monomer material is selected from amine, alcohols, ether with carbon-carbon double bond or oxygen-containing hat energy
Class or heterocyclic compound.Preferably, described amine, alcohols, ethers or heterocyclic compound include itaconic acid, amino acid, the last of the ten Heavenly stems two
One or more in acid, butanediamine, decamethylene diamine, furfuryl alcohol, aniline, pyrroles, thiophene, 2-3 dihydrofuran, or its aqueous solution.On
Compound is stated so that biomass water system convered structure system has good electric conductivity.
Further, described catalyst is to provide the catalyst system and catalyzing of Bronsted acid, selected from formic acid, acetic acid, oxalic acid, hydrochloric acid,
One or more in sulfuric acid or nitric acid.
The present invention also provides a kind of electrode liquid phase slurry, including electrode active material and appropriate deionized water, also includes
Biomass water system conductive bond system described in preceding solution, liquid phase slurry viscosity is in the range of 1-5000cps.Due to
The biomass water system conductive bond system that the present invention is provided has good wetability to electrode active material, therefore, electrode slurry
Material is easily well mixed, and mixed process can be completed within a short period of time.
The present invention also provides a kind of electrode, including electrode current collecting body, is also starched comprising electrode liquid phase described in preceding solution
Expect the electrode pastes for being formed.The electrode obtained lotion is coated with or is sprayed on electrode current collecting body surface, heated solidification, biomass
The in-situ cross-linked polymerization of monomer material.The polymer for being generated has carbon-carbon double bond structure, forms conjugated electrons to system, Ke Yiwei
Electron transmission provides path.The polymer is the conductive adhesive in electrode, completes the preparation of electrode, finally realizes the electricity of electrode
Chemical property and stable circulation performance.
The present invention also provides a kind of electrochmical power source, comprising the electrode described in preceding solution.Further, the chemistry
Power supply includes Ni-MH battery, lithium ion battery, ultracapacitor, sodium-ion battery, Magnesium ion battery or aluminium ion battery.
The present invention also provides a kind of preparation method of electrode described in preceding solution, including following preparation process：
(1) under 10~50 degrees Celsius, by the catalyst of 1~30% mass fraction be added to biomass liquid monomer or its
In the aqueous solution, catalyst is set to be completely dissolved wherein；
(2) in above-mentioned mixed solution, electrode active material is added, biomass monomer and active material mass ratio be 1~
30：100, mixed 1~60 minute under the certain mixing speed of high-speed homogenization machine, obtain uniform electrode pastes；
(3) the electrode obtained lotion is coated with or is sprayed on electrode current collecting body, biomass monomer is by the journey that is heating and curing
The in-situ cross-linked polymerization of sequence forms resinous polymer, and heating-up temperature is 50~200 degrees Celsius, and hardening time is 1~60 minute, heating
Solidification terminates to complete electrode slice preparation.Biomass monomer is passed through as the presoma of binding agent on electrode material granules surface
Cross cross-linking polymerization and progressively solidify to form resinous polymer.
Further, step (3) described resinous polymer has the π-pi-conjugated structure being made up of carbon-carbon double bond, and electronics is led
Electric rate is in the range of 1-10S/cm.
Further, step (3) the resinous polymer molecular weight ranges are 700-2000, and thermal stable temperature is 0-400
Degree Celsius.
Further, the mixing speed described in step (2) is 100-6000 rpms, and mixing time is 1-30 minutes.
Further, the spraying described in step (3) be by electrode pastes be sprayed on electrode current collecting body it is two-sided on, injection rate
It is 2-1000mg/ (minm2).Spraying process is distributed more compared to coating process, electrode active material in collection liquid surface
Uniformly, electrode preparation efficiency is higher.
Relative to the electrode fabrication or adhesive method announced at present, biomass water system conductive bond system has water concurrently
The advantages of system's safety, cheap environmental protection, conductive bond, process is simple.Details are as follows for beneficial effects of the present invention：
(1) patent expands the new application field of Biomass monomer material, is conducive to advancing the exploitation of biological material
And utilization.For example, biomass monomer material can come from stalk.At present, substantial amounts of stalk is embarrassed in what is nowhere utilized in agricultural
Border, Biomass liquid monomer material is processed using stalk, and its price and environmental protection are respectively provided with clear superiority.
(2) the biomass monomer for being used is water soluble liquid phase, it is to avoid conventional binders need to use organic solvent, pole
The big production cost for reducing electrochmical power source and cream technique, it is ensured that Environmental security and health of human body.Liquid phase described here
Monomer is including itaconic acid, amino acid, decanedioic acid, butanediamine, decamethylene diamine, furfuryl alcohol, aniline, pyrroles, thiophene, 2-3 dihydrofuran etc.
Amine, alcohols, ethers and heterocyclic compound containing carbon-carbon double bond.
(3) using biomass water system conductive bond system, the preparation process of its electrode slurry and pole piece is relative to traditional
Method also has improvement to act on, and its effect is：The liquid monomer has good wetability with numerous electrode materials.Excellent profit
The moist mixing efficiency that can improve material and liquid phase, reduces mixing time, it is to avoid the material such as other surfactants of addition,
For the quick cream technique that closes provides technical guarantee.Relative to the technology for preparing electrode announced, its only in slurry and cream stage, just
Needing the incorporation time of a few hours, biomass water system conductive bond system has huge jump.
(4) biomass water system conductive bond system is relied on, such monomer can complete polymerisation under catalysts conditions.
In 0-120 degree Celsius ranges, hardening time, catalytic condition was simple in 1-60 minutes for catalytic temperature, will simplify electrode and prepares
Process.Gained slurry is sprayed on electrode current collecting body surface, and, compared to coating process, electrode active material is in afflux for spraying process
Body surface EDS maps are more uniform, and electrode preparation efficiency is higher.After being heating and curing, electrode is compacted by rolling, wholeization
Learn power supply from dispensing and cream, spray in flakes, the preparation process less than 30 minutes, whole electrode slice is prepared and conductive adhesive
Synthesis is completed simultaneously.Catalyst described here refers to the catalyst system and catalyzing that can provide Bronsted acid, organic acid have formic acid, acetic acid and
Oxalic acid etc., inorganic acid has hydrochloric acid, sulfuric acid and nitric acid etc..These catalyst are cheap and are easily obtained.
(5) a big advantage of biomass water system conductive bond system is that binding agent is formed in electrode solidification process
's.In-situ solidifying process is cross-linked with each other between promoting liquid monomer, forms a firm coherent network.According to nano-indenter test
Technology and electrolyte immersion test show that the in-situ polymerization bonder for being formed, its mechanical strength is bonded more than existing PVdF
System, while having certain elasticity.The system not only increases the binding ability of electrode active material and binding agent, is also lifted
The bond strength of electrode active material and collector, it is ensured that the cycle performance of electrode active material and electrode.Meanwhile, it is in situ
The polymeric binder for generating that is polymerized has good chemical stability and heat endurance：It is acidproof, alkaline-resisting, corrosion-resistant, do not dissolve in
Organic solvent system and by heat decomposition temperature be more than 200 DEG C.
(6) abundant carbon-carbon double bond π-pi-conjugated structure, the electricity of p tracks are contained in the resinous polymer of in-situ polymerization generation
Sub- cloud has the overlap of part, therefore, the resinous polymer has certain electron transmission ability.Using the polymer as electrode
Binding agent, it will help to reduce the use of conductive additive in electrode, or do not use conductive additive.For ferric phosphate
The traditional electrode active material such as lithium, the non-electroactive content of material in electrode is reduced to below 5wt.%, for high power capacity
Silicon and sulfur electrode material, the non-electroactive content of material in electrode is reduced to below 20wt.%, and these numerical indications are equal
Better than the electrode preparation method announced.The content of the non-electroactive material in electrode is reduced, the energy of electrode is improve
Metric density and power-performance, this is substantial contribution of the biomass water system conductive bond system for electrochmical power source.
Brief description of the drawings
Fig. 1 be traditional handicraft Kynoar bonding system prepare ferrous phosphate lithium electrode (without conductive additive) it is long when
Between soak electrolyte after picture.
Fig. 2 soaks for a long time for the ferrous phosphate lithium electrode of the biomass water system conductive bond system preparation that the present invention is provided
Picture after electrolyte.
Fig. 3 is the ferrous phosphate for being prepared with biomass water system conductive bond system and poly- inclined tetrafluoroethene bonding system respectively
The 0.17C rate charge-discharge curve comparison figures of lithium electrode (without conductive additive).
Fig. 4 is the 0.5C of the ferrous phosphate lithium electrode (without conductive additive) prepared with biomass water system conductive bond system
Rate charge-discharge circulation volume figure, electrode load amount is 51.9g/cm2。
Specific embodiment
The present invention is made below in conjunction with accompanying drawing being further illustrated.
Embodiment 1
Lithium-ion battery system.The based lithium-ion battery positive plate of biomass water system conductive bond systems and the application system
Preparation method, completes according to following steps：
1. under 10~80 degrees Celsius, the oxalic acid of 5% mass fraction will be added to be added in the monomer of liquid phase, treat catalyst
It is completely dissolved.
2. in above-mentioned mixed solution, electrode lithium iron phosphate cathode material, monomer and active material mass ratio are added
It is 20:100, mixed 5 minutes by high-speed homogenization machine, obtain uniform electrode pastes.
3. the electrode obtained lotion is coated or is sprayed on electrode current collecting body, by the program of being heating and curing, heating-up temperature
It it is 80~140 degrees Celsius, hardening time is 30 minutes, and lithium ion cell electrode piece completes preparation.
In this implementation, content of the polymeric binder for being generated in pole piece is measured as the quality point of 3.8wt.%
Number.
Comparative example 1
Using Kynoar (PVdF) bonding system and cream, the quality proportioning of binding agent and active material is with reference to example 1
In each component quality condition.
1. the PVdF binding agents of 3.8% mass fraction are dissolved in 10 milliliters of organic solvent N- hydroxymethylpyrrol alkanones
In, 96.2% ferrousphosphate lithium material is added, stir 10 hours.
2. well mixed lotion is coated in metal collector, vacuum drying, completes LiFePO 4 electrode slice
Prepare.
Found by the electrode blade technolgy and process prepared to both the above bonding system：Biomass water system conductive bond
System takes about 35 minutes altogether, and Kynoar bonding system then needs the time of ten a few houres.Biomass water system is conductive viscous
The knot body system used time is short, simple to operate.Additionally, compared to the organic system of Kynoar cohesive body agent, biomass water system is conductive
Bonding system is more environmentally friendly, with low cost.
Using the electrode slice prepared by two kinds of bonding technologies, after being soaked in organic electrolyte, Kynoar is bonded
System surface effect is as shown in figure 1, biomass water system conductive bond system surface effect is as shown in Figure 2.Led with biomass water system
LiFePO 4 electrode slice prepared by electric bonding system remains on good bond effect, but uses PVdF bonding systems
Electrode slice occur in that electrode powder depart from situation.This shows biomass water system conductive bond system and existing lithium ion battery
The component such as organic solvent and electrolytic salt does not react mutually, good thermal stability, better than PVdF bonding systems.
In electro-chemical test, as shown in figure 3, in the case where any conductive agent is not added with, biomass water system is conductive viscous
The conductive characteristic that knot body system has, helps LiFePO 4 electrode material to give play to normal chemical property.However, due to
PVdF inherently insulators, in the case where not there is conductive additive, the overall electric conductivity of electrode is not good, and internal resistance polarization is big,
Ferrousphosphate lithium material cannot give play to its due capacity.Especially under 0.17C multiplying powers, its charge/discharge capacity is only this hair
/ 3rd of bright binding agent.
Embodiment 2
Lithium-ion battery system.The based lithium-ion battery positive plate of biomass water system conductive bond systems and the application system
Preparation method, completes according to following steps：
1. under 10~80 degrees Celsius, preferably 40 degrees Celsius, the oxalic acid of 10% mass fraction will be added to be added to liquid phase
In monomer, treat that catalyst is completely dissolved.
2. in above-mentioned mixed solution, lithium iron phosphate cathode material is added, monomer is 20 with active material mass ratio:
100, mixed 5 minutes by high-speed homogenization machine, obtain uniform electrode pastes.
3. the electrode obtained lotion is coated or is sprayed on electrode current collecting body, by the program of being heating and curing, heating-up temperature
It it is 120 degrees Celsius, hardening time is 30 minutes, and lithium ion cell electrode piece had both completed preparation.
Compared to embodiment 1, temperature is the important parameter for controlling catalyst dissolution and catalytic effect.
The catalyst dissolution process of first stage：At a lower temperature, catalyst dissolution is slower, monomer rate of polymerization also phase
To relatively slow, overall preparation process is influenceed.But, in the case where temperature is higher, the rate of polymerization of monomer is too fast, and monomer is not obtained
It is mixed thoroughly with active material, the polymerization of monomer material have impact on overall adhesive property, the machinery for reducing electrode is strong
Degree.It is therefore preferable that under 30-60 degrees celsius, wherein 40 degrees Celsius is optimal, in catalyst-solvent to liquid monomer.
The curing process of second stage：Solidification temperature is more than 140 degrees Celsius, and monomer is readily volatilized, causes remaining bonding
Agent content is too low；Solidification temperature is less than 100 degrees Celsius, reduces the activity of catalyst monomer polymerization, causes monomer cure
Time is more long, is difficult to control the effect for bonding.In Optimal Experimental, it is optimal to use 120 degrees Celsius of solidification temperatures.
In addition, selected temperature range can control mass fraction of the generated polymeric binder in pole piece to be less than
5%, the activity substance content in electrode is effectively raised, improve the energy density of electrode.
Using the implementation 2 of optimization, following for LiFePO 4 electrode slice prepared by biomass water system conductive bond system is relied on
Ring property is as shown in figure 4, under 0.5C multiplying powers, the LiFePO 4 electrode slice stable circulation using in-situ polymerization bonder exceedes
180 circles.Capability retention is 97% or so.
Embodiment 3
Lithium-ion battery system.The based lithium-ion battery positive plate of biomass water system conductive bond systems and the application system
Preparation method, completes according to following steps：
1. at 20 degrees celsius, the formic acid of 30% mass fraction will be added to be added in the monomer of liquid phase, be well mixed.
2. in above-mentioned mixed solution, electrode lithium cobaltate cathode material is added, monomer is 10 with active material mass ratio:
100, mix 10 minutes, obtain uniform electrode pastes.
3. the electrode obtained lotion is coated or is sprayed on electrode current collecting body, by the program of being heating and curing, heating-up temperature
It it is 120 degrees Celsius, hardening time is 60 minutes, and lithium ion cell electrode piece completes preparation.
Using cobalt acid lithium as active material, in the case of without any conductive agent, the specific capacity of electrode 5C multiplying powers
Higher than 100mAh/g.
Embodiment 4
Lithium-ion battery system.The anode plate for lithium ionic cell of biomass water system conductive bond systems and the application system
Preparation method, completes according to following steps：
1. at 60 c, the sulfuric acid of 1% mass fraction will be added to be added in the monomer of liquid phase, be well mixed.
2. in above-mentioned mixed solution, electrode graphite negative material is added, monomer is 20 with active material mass ratio:
100, mix 10 minutes, obtain uniform electrode pastes.
3. the electrode obtained lotion is coated or is sprayed on electrode current collecting body, by the program of being heating and curing, heating-up temperature
It it is 100 degrees Celsius, hardening time is 10 minutes, and lithium ion cell electrode piece completes preparation.
Using graphite cathode as active material, in the case of without any conductive agent, the specific capacity of 0.1C multiplying powers
Higher than 350mAh/g.
Embodiment 5
Lithium-ion battery system.The anode plate for lithium ionic cell of biomass water system conductive bond systems and the application system
Preparation method, completes according to following steps：
1. at 60 c, the hydrochloric acid of 5% mass fraction will be added to be added in the monomer of liquid phase, be well mixed.
2. in above-mentioned mixed solution, electrode silica powder anode material and 20% conductive additive, monomer and work are added
Property material mass ratio be 30:100, mix 60 minutes, obtain uniform electrode pastes.
3. the electrode obtained lotion is coated or is sprayed on electrode current collecting body, by the program of being heating and curing, heating-up temperature
It it is 80~150 degrees Celsius, hardening time is 30 minutes, and lithium ion cell electrode piece completes preparation.
Up to 1000 circles, capacity is higher than 1000 every milligram of MAHs, inert matter to the silicon electrode cycle-index for being obtained
Mass fraction in electrode is less than 30%.
Embodiment 6
Super capacitor system.The preparation side of biomass water system conductive bond system and the condenser plate using the system
Method, completes according to following steps：
1. at 20 degrees celsius, the formic acid of 10% mass fraction will be added to be added in the monomer of liquid phase, be well mixed.
2. in above-mentioned mixed solution, electrode for capacitors active material is added, monomer is 30 with active material mass ratio:
100, mix 20 minutes, obtain uniform electrode pastes.
3. the electrode obtained lotion is coated or is sprayed on electrode current collecting body, by the program of being heating and curing, heating-up temperature
It it is 80 degrees Celsius, hardening time is 30 minutes, and lithium ion cell electrode piece completes preparation.
Ultracapacitor active material has electric double layer including porous carbon, activated carbon, carbon black, CNT, Graphene etc.
The carbon material of characteristic；Manganese dioxide, manganese oxide, nickel oxide, nickel hydroxide, cobalt oxide, cobalt sesquioxide etc. have fake capacitance special
The metal oxide of property；The organic polymer with fake capacitance characteristic such as polyaniline and polypyrrole.The above ultracapacitor
Biomass water system conductive bond system can use to be bonded, its electrochemical performance is in particular in that energy density is high, work(
Rate performance is good, has extended cycle life.
Embodiment 7
Sodium-ion battery system.The biomass water system conductive bond system of specific embodiment 7 and application the system sodium from
The preparation method of sub- battery pole piece, completes according to following steps：
1. under 30 degrees Celsius, the acetic acid of 10% mass fraction will be added to be added in the monomer of liquid phase, treat that catalyst is complete
CL.
2. in above-mentioned mixed solution, sodium-ion battery electrode active material, monomer and active material mass ratio are added
It is 30:80, mix 10 minutes, obtain uniform electrode pastes.
3. the electrode obtained lotion is coated or is sprayed on electrode current collecting body, by the program of being heating and curing, heating-up temperature
It it is 100 degrees Celsius, hardening time is 30 minutes, and lithium ion cell electrode piece completes preparation.
The sodium ion battery electrode material metal oxide with deintercalation sodium ion such as including cobalt acid sodium；Vanadium phosphate sodium and phosphorus
The phosphate with deintercalation sodium ion such as sour ferrisodium；The carbon with deintercalation sodium ion such as Graphene, CNT and pyrolytic carbon
Material.
Embodiment 8
The binder system is applied to Magnesium ion battery, and remaining implementation condition is with reference to embodiment 2~5.
Embodiment 9
The binder system is applied to aluminium ion battery, and remaining implementation condition is with reference to embodiment 2~5.
Claims (14)
1. a kind of biomass water system conductive bond system, comprising：Biomass monomer material and catalyst, it is characterised in that institute
The biomass monomer material stated is soluble water system.
2. biomass water system conductive bond system as claimed in claim 1, it is characterised in that described biomass monomer material
Selected from the amine with carbon-carbon double bond or oxygen-containing functional group, alcohols, ethers or heterocyclic compound.
3. biomass water system conductive bond system as claimed in claim 2, it is characterised in that described amine, alcohols, ethers
Or heterocyclic compound includes itaconic acid, amino acid, decanedioic acid, butanediamine, decamethylene diamine, furfuryl alcohol, aniline, pyrroles, thiophene, 2-3 bis-
It is a kind of, various in hydrogen furans, or its aqueous solution.
4. biomass water system conductive bond system as claimed in claim 1, it is characterised in that described catalyst is to provide matter
The catalyst system and catalyzing of sub- acid, selected from one or more in formic acid, acetic acid, oxalic acid, hydrochloric acid, sulfuric acid or nitric acid.
5. a kind of electrode liquid phase slurry, including electrode active material and appropriate deionized water, it is characterised in that also comprising right
It is required that the biomass water system conductive bond system described in 1~4 any claim, liquid phase slurry viscosity is in 1~5000cps models
In enclosing.
6. a kind of electrode, including electrode current collecting body, it is characterised in that also comprising as electrode liquid phase slurry shape described in claim 5
Into electrode pastes.
7. a kind of electrochmical power source, it is characterised in that comprising the electrode described in claim 6.
8. electrochmical power source as claimed in claim 7, it is characterised in that the electrochmical power source includes Ni-MH battery, lithium-ion electric
Pond, ultracapacitor, sodium-ion battery, Magnesium ion battery or aluminium ion battery.
9. a kind of preparation method of electrode as claimed in claim 6, it is characterised in that including following preparation process：
(1) under 10~80 degrees Celsius, the catalyst of 1~30% mass fraction is added to biomass liquid monomer or its is water-soluble
In liquid, catalyst is set to be completely dissolved wherein；
(2) in above-mentioned mixed solution, electrode active material is added, biomass monomer is 1~30 with active material mass ratio:
100, mixed 1~60 minute under the certain mixing speed of high-speed homogenization machine, obtain uniform electrode pastes；
(3) the electrode obtained lotion is coated with or is sprayed on electrode current collecting body, biomass monomer is former by the program that is heating and curing
Position cross-linked polymeric forms resinous polymer, and heating-up temperature is 50~200 degrees Celsius, and hardening time is 1~60 minute.
10. preparation method as claimed in claim 9, it is characterised in that step (1) solution temperature is 30~60 degrees Celsius, step
Suddenly (3) heating-up temperature is 100~140 degrees Celsius.
11. preparation methods as claimed in claim 9, it is characterised in that step (3) described resinous polymer has double by carbon carbon
π-pi-conjugated the structure of key composition, electronic conductivity is in the range of 1~10S/cm.
12. preparation methods as claimed in claim 9, it is characterised in that step (3) the resinous polymer molecular weight ranges are
700~2000, thermal stable temperature is 0~400 degree Celsius.
13. preparation methods according to claim 9, it is characterised in that mixing speed described in step (2) for 100~
6000 rpms, mixing time is 1~30 minute.
14. preparation methods according to claim 9, the spraying described in step (3) is that electrode pastes are sprayed on into electrode collection
On fluid is two-sided, injection rate is 2~1000mg/ (minm2)。
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