CN106025283B - The aqueous adhesive of lignin-base for negative electrode of lithium ion battery and the electrode slice and lithium ion battery based on it - Google Patents
The aqueous adhesive of lignin-base for negative electrode of lithium ion battery and the electrode slice and lithium ion battery based on it Download PDFInfo
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- CN106025283B CN106025283B CN201610357495.2A CN201610357495A CN106025283B CN 106025283 B CN106025283 B CN 106025283B CN 201610357495 A CN201610357495 A CN 201610357495A CN 106025283 B CN106025283 B CN 106025283B
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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
- H01M4/621—Binders
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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
- H01M4/139—Processes of manufacture
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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 belongs to technical field of lithium ion, a kind of aqueous adhesive of the lignin-base for negative electrode of lithium ion battery and negative electrode of lithium ion battery electrode slice and lithium ion battery based on it are disclosed.The aqueous adhesive of the lignin-base includes the component of following parts by weight: 100 parts of water-soluble lignin；20~1000 parts of butadiene-styrene rubber.The present invention also provides a kind of negative electrode of lithium ion battery electrode slices and its lithium ion battery based on above-mentioned adhesive.The aqueous adhesive of lignin-base of the present invention is applied to negative electrode of lithium ion battery, increase the dispersibility and cohesive force of electrode material, effectively overcome the reunion of active material, improve coating uniformity of the electrode slurry on Cu foil, electrode material good toughness, its interface impedance can be reduced, negative electrode sheet resistance, the larger high rate capability for improving material are reduced；On the other hand, lignin provided by the invention derives from natural plants extensively, environmentally protective, can significantly reduce the cost of battery applied to water system adhesive.
Description
Technical field
The invention belongs to technical field of lithium ion, in particular to a kind of lignin-base for negative electrode of lithium ion battery
Aqueous adhesive and negative electrode of lithium ion battery electrode slice and lithium ion battery based on it.
Background technique
Though adhesive is the non-active ingredient in lithium ion cell electrode piece, but preparing lithium ion cell electrode piece must
One of the important materials that must be used.In the electrodes, adhesive had both played the cohesive action of active material interlayer, was also used for active material
Cohering between the bed of material and collector.In addition to caking property, adhesive also need to have flexibility, the indissolubility in electrolyte,
Compactness, chemistry and electrochemical stability and be easy to electrode coating.The adhesive of optimised quantity is added, biggish appearance can be obtained
Amount, longer cycle life and lower internal resistance, this is to cycle performance, fast charging and discharging ability and the reduction electricity for improving battery
The internal pressure in pond etc. has facilitation.
Traditional organic solvent type fluorine-containing adhesive Kynoar (PVDF) is widely applied in commodity production battery, but
Its is hygroscopic, molecular weight and molecular weight after water suction, and bond performance is deteriorated；It is easy to be swollen by nonaqueous phase electrolyte, is collecting electrode material
Bond performance is deteriorated on fluid；And make dispersing agent usually using volatile, inflammable and explosive, toxic organic solvent, these have
Solvent is not only expensive but also seriously pollutes environment.Compared with organic solvent type adhesive, aqueous adhesive has without molten
Agent release, it is environmentally friendly, at low cost, non-ignitable, using it is safe the features such as, become the important development side of lithium ion battery adhesive industry
To.
With deepening continuously for people's research, rapid development, and its type is had been obtained in aqueous adhesive at present
Also more and more.The aqueous adhesive reported at present mainly includes phenolic resin type, amino resin type, polyacrylic acid epoxy-type, rubber
Glue-type emulsion glue, ethylene-acetate second epoxy-type, sodium carboxymethylcellulose, sodium alginate, pectic acid sodium, chitosan etc..Particularly,
In current scale commodity production, the manufacture of graphite negative electrode of lithium ion battery piece oneself through using sodium carboxymethylcellulose (CMC)/
This kind of aqueous adhesive of butadiene-styrene rubber (SBR).However, electrolyte is formed when graphite cathode adhesive aqueous using CMC/SBR
The impedance of " solid electrolyte membrane " (Solid Electrolyte Interface) is larger, is unfavorable for the deintercalation of lithium ion, influences
The long-term cycle performance and high rate capability (J.Power Sources, 2005,147,249-255) of battery.
Lignin is a kind of aromatic series natural polymer, is the biomass that content is only second to cellulose in nature
Resource has tridimensional network, is a kind of typical containing a variety of functional groups such as phenolic hydroxyl group, alcoholic extract hydroxyl group, carboxyl and methoxyl group
Amphipathy macromolecule.Lignin is that one kind is widely present in the intracorporal native hydrocarbon of plant, and content reaches in wood
20~35%, up to 15~25% in herbaceous plant.Lignin have it is nontoxic, do not crystallize, be heat-resisting, is fast light, is anti-aging, bonding force
By force, many advantages, such as good biocompatibility.
Industrial lignin mainly includes water from the waste in the fields such as pulping and paper-making, wood hydrolysis, biomass energy
The lignosulfonates of dissolubility, water-soluble poor alkali lignin and enzymolysis xylogen.However, a large number of studies show that, it can pass through
The reactions such as sulfonation or carboxylated assign alkali lignin and the good water solubility of enzymolysis xylogen.These water-soluble lignin have
Good absorption and dispersion performance are widely used in many solids such as cement, pesticide, water-coal-slurry, dyestuff and conducting polymer
Dispersion in grain suspension system.It is well known that the quality of negative electrode active material dispersion, directly affects the property of entire lithium ion battery
Energy.Up to the present, not yet studies have reported that water-soluble lignin is used for the dispersion of lithium ion battery electrode material and is cohered.
Summary of the invention
In order to overcome the shortcomings and deficiencies of the prior art described above, the primary purpose of the present invention is that provide it is a kind of for lithium from
The aqueous adhesive of the lignin-base of sub- battery cathode.
It is negative that another object of the present invention is to provide a kind of lithium ion batteries based on the aqueous adhesive of above-mentioned lignin-base
Pole electrode slice.
A further object of the present invention is to provide a kind of lithium ion batteries containing above-mentioned negative electrode of lithium ion battery electrode slice.
The purpose of the present invention is realized by following proposal:
A kind of aqueous adhesive of lignin-base for negative electrode of lithium ion battery, the component including following parts by weight:
100 parts of water-soluble lignin
20~1000 parts of butadiene-styrene rubber (SBR).
The water-soluble lignin includes lignosulfonates, and with alkali lignin or enzymolysis xylogen is main former
Expect, at least one of modified product obtained from chemically modified access sulfonic group, carboxyl, ammonium (amine) base isoreactivity group.
Preferably, the water-soluble lignin include lignosulfonates, sulfonated wheat-strew lignin, sulfonation enzymatic hydrolysis it is wooden
Element, carboxylated alkali lignin, carboxylated enzymolysis xylogen, ammonium (amine) choline lignin and ammonium (amine) are changed in enzymolysis xylogen extremely
Few one kind, the dosage of each component can be arbitrary proportion.
The present invention also provides a kind of negative electrode of lithium ion battery electrode slices based on the aqueous adhesive of above-mentioned lignin-base.
The negative electrode of lithium ion battery electrode slice is used as using the aqueous adhesive of lignin-base as described above and is cohered
Agent.It include active material, conductive agent and the aqueous adhesive of lignin-base in the component of the negative electrode of lithium ion battery electrode slice.
Preferably, active material, conductive agent and the aqueous adhesive of lignin-base in the negative electrode of lithium ion battery electrode slice
Mass ratio be (70~95): (1~20): (4~10).
The active material is this field traditional lithium-ion battery electrode active material, can be graphite, activity
At least one of charcoal, carbonaceous mesophase spherules and silicon/carbon complex.
The conductive agent is this field conventional conductive agent, such as conductive black (Super P).
The preparation method of the negative electrode of lithium ion battery electrode slice the following steps are included:
By in the aqueous adhesive of lignin-base water-soluble lignin, conductive agent, active material, lignin-base is aqueous coheres
SBR in agent is sequentially added in water, is stirred evenly, and electrode slurry can be obtained, it is coated on Cu foil, dry, rolling, i.e.,
Obtain negative electrode of lithium ion battery electrode slice.
Preferably, the solid content of the electrode slurry is 30~70wt%.
Preferably, the condition of the drying is that constant-temperature vacuum dries 12~48h at 80~120 DEG C.
Further, the present invention also provides a kind of lithium ions containing negative electrode of lithium ion battery electrode slice as described above
Battery.
Lithium ion battery as described above includes battery case, pole piece and electrolyte, and the pole piece and electrolyte are sealed in
In battery case, the pole piece include the as described above electrode slice including the aqueous adhesive of lignin-base, lithium piece to electrode and
Diaphragm between electrode.
Mechanism of the invention are as follows:
The aqueous adhesive of lignin-base is applied in negative electrode of lithium ion battery by the present invention, and it is forthright to be obviously improved its high power
It can and reduce its impedance.By adsorbing water-soluble lignin on negative electrode active material particle surface, in conjunction with lignin itself
Three-dimensional space network structure is formed by steric hindrance effect, can be efficiently against the reunion between active material particle；Simultaneously
A large amount of existing sulfonic groups, carboxyl or ammonium (amine) base are adsorbed in the water-soluble lignin on active material particle surface, it can
Hydrogen bond action is formed between hydrone, so that active material particle can be uniformly and stably dispersed in water；Furthermore
Hydrophobic core can form bridge linking effect between active material particle in water-soluble lignin, substantially increase between active material
Cohesive force.Therefore, it selects water-soluble lignin and butadiene-styrene rubber (SBR) to compound to use as adhesive, on the one hand, increase electricity
The dispersibility and cohesive force of pole active material improve coating uniformity of the electrode slurry on Cu foil, reduce negative electrode
Sheet resistance improves the high rate capability of lithium ion battery；On the other hand, the cost of lithium ion battery is significantly reduced.
The present invention compared with the existing technology, have the following advantages and the utility model has the advantages that
Water-soluble lignin and butadiene-styrene rubber (SBR) being used in compounding and using in the aqueous adhesive of lignin-base of the present invention
The selection of amount is applied to negative electrode of lithium ion battery, increases the dispersibility and cohesive force of electrode material, electrode material good toughness,
Its interface impedance, the larger high rate capability for improving material can be reduced；On the other hand, the extensive source of lignin provided by the invention
It is environmentally protective in natural plants, it can significantly reduce the cost of battery applied to water system adhesive.
Detailed description of the invention
Fig. 1 is the outside drawing of 1 graphite cathode of the embodiment of the present invention and comparison electrode pole piece.
Fig. 2 is the high rate performance figure of 1 graphite cathode of the embodiment of the present invention and comparison electrode.
Fig. 3 is the AC impedance figure of 1 graphite cathode of the embodiment of the present invention and comparison electrode.
Fig. 4 is the high rate performance figure of 2 activated carbon negative electrode of the embodiment of the present invention.
Fig. 5 is the high rate performance figure of 3 carbonaceous mesophase spherules cathode of the embodiment of the present invention.
Fig. 6 is 4 silicon of the embodiment of the present invention/carbon complex cathode high rate performance figure.
Fig. 7 is the outside drawing after 1 graphite cathode slurry of comparative example of the present invention coating is dry.
Fig. 8 is the AC impedance figure of 2 graphite cathode of comparative example of the present invention.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Reagent used in the following example can be commercially available from commercial channel.
Embodiment 1
1, the preparation of electrode is tested:
The mass ratio of graphite, conductive black (Super P) and the aqueous adhesive of lignin-base is 85:6:9.Lignin-base water
Property adhesive in the mass ratio of water-soluble lignin (sodium lignin sulfonate) and SBR be 2:1.It will be in the aqueous adhesive of lignin-base
Water-soluble lignin be added in appropriate deionization, stirring dissolve it sufficiently；It is resulting that conductive black is added to upper step
In water-soluble lignin aqueous solution, it is stirred until homogeneous dispersion；Graphite is added in the resulting mixture of upper step, is stirred until homogeneous
Dispersion；SBR in the aqueous adhesive of lignin-base is added in the resulting mixture of upper step, dispersion is stirred until homogeneous, obtains
Electrode slurry (solid content 60%)；Obtained electrode slurry is evenly applied on Cu foil, 100 DEG C of vacuum drying, rolling, i.e.,
Obtain graphite negative electrode of lithium ion battery electrode slice.After the pole piece cut-parts being dried in vacuo weighing, it is assembled in glove box
It is to electrode, using polyethylene film as diaphragm, with 1M LiPF with lithium piece in 2032 battery cases6EC/DMC/DEC (v/v/v=1/1/
It 1) is electrolyte assembled battery.
2, the preparation of comparison electrode:
Using CMC/SBR as adhesive, comparison electrode is prepared in the same way.
3, electro-chemical test:
The test of carry out rate charge-discharge and testing impedance to test electrode, comparison electrode.
4, partial size is tested:
The average grain diameter of graphite when testing water-soluble lignin and CMC respectively as dispersing agent by laser particle analyzer.
5, interpretation of result:
Fig. 1 is the outside drawing of the present embodiment graphite cathode and comparison electrode pole piece.It will be seen from figure 1 that water-soluble wooden
The coating homogeneity for the graphite cathode pole piece that element/SBR is prepared as adhesive and the toughness of pole piece are made with commercialization CMC/SBR
Graphite cathode pole piece for adhesive preparation is suitable, shows a possibility that water-soluble lignin/SBR is as adhesive on a macro scale.
Fig. 2 be the present embodiment test electrode and comparison electrode rate charge-discharge curve, table 1 be its corresponding initial charge specific capacity and
The average grain diameter of graphite when first charge-discharge efficiency and water-soluble lignin and CMC are respectively as dispersing agent.It can be with from table
Find out, uses water-soluble lignin/SBR as the initial charge specific capacity of the graphite electrode of adhesive for 360.3mAhg-1、
First charge discharge efficiency is 89.7%, is above the initial charge specific capacity 339.3mAhg of CMC/SBR-1, first charge discharge efficiency 86.3%.And
And water-soluble lignin as dispersing agent when (20 μm) of average grain diameter of graphite graphite when being less than CMC as dispersing agent average grain
Diameter (39 μm), shows that water-soluble lignin is advantageous compared with CMC in terms of dispersed graphite.In addition, figure it is seen that using water
The graphite electrode that dissolubility lignin/CMC is prepared as adhesive, when current strength reaches 2C, specific capacity is
253.7mAh·g-1, much higher than the specific capacity 112.7mAhg of CMC/SBR adhesive graphite electrode-1.Fig. 3 be test electrode and
The AC impedance figure for the first time of comparison electrode, as seen from the figure, the graphite electricity prepared using water-soluble lignin/SBR as adhesive
The charge migration resistance of pole is significantly less than charge migration resistance of the CMC/SBR as adhesive graphite electrode.
The performance parameter of the graphite cathode material of the different adhesives of table 1
Embodiment 2
1, the preparation of electrode is tested:
The present embodiment the difference from embodiment 1 is that, test electrode is also using the aqueous adhesive of lignin-base as glutinous
Agent is tied, but using active carbon as active material.Active carbon, conductive black (Super P) and the aqueous adhesive of lignin-base
Mass ratio is 75:15:10.Water-soluble lignin (calcium lignosulfonate and sulfonated wheat-strew lignin in the aqueous adhesive of lignin-base
Binary mixture) and SBR mass ratio be 3:1.Water-soluble lignin in the aqueous adhesive of lignin-base is added to suitable
It measures in deionization, stirring dissolves it sufficiently；Conductive black is added in the resulting lignin aqueous solution of upper step, is stirred to equal
Even dispersion；Active carbon is added in the resulting mixture of upper step, dispersion is stirred until homogeneous；It will be in the aqueous adhesive of lignin-base
SBR be added in the resulting mixture of step, be stirred until homogeneous dispersion, obtain electrode slurry (solid content 40%)；Will
To electrode slurry be evenly applied on Cu foil, 100 DEG C vacuum drying, roll to get lithium ion battery activated carbon negative electrode electrode
Piece.After the pole piece cut-parts being dried in vacuo weighing, it is assembled in 2032 battery cases in glove box, is to electricity with lithium piece
Pole, using polyethylene film as diaphragm, with 1M LiPF6EC/DMC/DEC (v/v/v=1/1/1) is electrolyte assembled battery.
2, electro-chemical test:
Rate charge-discharge test is carried out to test electrode.
3, interpretation of result:
Fig. 4 is that the present embodiment tests electrode rate charge-discharge curve.Figure 4, it is seen that using water-soluble lignin/
Activated carbon electrodes of the SBR as adhesive, when current strength reaches 2C, charge specific capacity still maintains 139.3mAhg-1。
Embodiment 3
1, the preparation of electrode is tested:
The present embodiment the difference from embodiment 1 is that, test electrode is also using the aqueous adhesive of lignin-base as glutinous
Agent is tied, but using carbonaceous mesophase spherules as active material.Carbonaceous mesophase spherules, conductive black (Super P) and lignin-base
The mass ratio of aqueous adhesive is 80:10:10.Water-soluble lignin (sodium lignin sulfonate, sulphur in the aqueous adhesive of lignin-base
Change enzymolysis xylogen and carboxylated alkali lignin ternary mixture) and SBR mass ratio be 1:3.Lignin-base is aqueous glutinous
Water-soluble lignin in knot agent is added in appropriate deionization, and stirring dissolves it sufficiently；Conductive black is added to upper step
In resulting lignin aqueous solution, it is stirred until homogeneous dispersion；Carbonaceous mesophase spherules are added in the resulting mixture of upper step, are stirred
It mixes to evenly dispersed；SBR in the aqueous adhesive of lignin-base is added in the resulting mixture of upper step, is stirred until homogeneous point
It dissipates, obtains electrode slurry (solid content 45%)；Obtained electrode slurry is evenly applied on Cu foil, 100 DEG C of vacuum drying,
Rolling is to get lithium ion battery carbonaceous mesophase spherules negative electricity pole piece.By the pole piece cut-parts being dried in vacuo weighing after, by its
It is assembled in glove box in 2032 battery cases, is to electrode, using polyethylene film as diaphragm, with 1M LiPF with lithium piece6EC/DMC/
DEC (v/v/v=1/1/1) is electrolyte assembled battery.
2, electro-chemical test:
Rate charge-discharge test is carried out to test electrode.
3, interpretation of result:
Fig. 5 is that the present embodiment tests electrode rate charge-discharge curve.From figure 5 it can be seen that using water-soluble lignin/
Carbonaceous mesophase spherules electrode of the SBR as adhesive, when current strength reaches 2C, charge specific capacity is still maintained
150.2mAh·g-1。
Embodiment 4
1, the preparation of electrode is tested:
The present embodiment the difference from embodiment 1 is that, test electrode is also using the aqueous adhesive of lignin-base as glutinous
Agent is tied, but using silicon/carbon complex as active material.Silicon/carbon complex, conductive black (Super P) and lignin-base water
Property adhesive mass ratio be 90:5:5.Water-soluble lignin (carboxylated enzymolysis xylogen, ammonium in the aqueous adhesive of lignin-base
The ternary mixture of choline lignin and amination enzymolysis xylogen) and SBR mass ratio be 2:3.It coheres lignin-base is aqueous
Water-soluble lignin in agent is added in appropriate deionization, and stirring dissolves it sufficiently；Conductive black is added to upper step institute
In the lignin aqueous solution obtained, it is stirred until homogeneous dispersion；Silicon/carbon complex is added in the resulting mixture of upper step, is stirred
It is extremely evenly dispersed；SBR in the aqueous adhesive of lignin-base is added in the resulting mixture of upper step, is stirred until homogeneous point
It dissipates, obtains electrode slurry (solid content 35%)；Obtained electrode slurry is evenly applied on Cu foil, 100 DEG C of vacuum drying,
Rolling is to get lithium ion battery silicon/carbon complex negative electricity pole piece.By the pole piece cut-parts being dried in vacuo weighing after, by its
It is assembled in glove box in 2032 battery cases, is to electrode, using polyethylene film as diaphragm, with 1M LiPF6EC/DMC/ with lithium piece
DEC (v/v/v=1/1/1) is electrolyte assembled battery.
2, electro-chemical test:
Rate charge-discharge test and testing impedance are carried out to test electrode.
3, interpretation of result:
Fig. 6 is that the present embodiment tests electrode rate charge-discharge curve.From fig. 6 it can be seen that using water-soluble lignin/
Silicon/carbon complex electrode of the SBR as adhesive, when current strength reaches 2C, charge specific capacity is still maintained
223.8mAh·g-1。
Comparative example 1
1, the preparation of electrode is tested:
The mass ratio of graphite, conductive black (Super P) and the aqueous adhesive of lignin-base is 85:6:9.Lignin-base water
Water-soluble lignin (binary mixture of sodium lignin sulfonate and sulfonated wheat-strew lignin) and the mass ratio of SBR are in property adhesive
6:1.Water-soluble lignin in the aqueous adhesive of lignin-base is added in appropriate deionization, stirring dissolves it sufficiently；
Conductive black is added in the resulting lignin aqueous solution of upper step, dispersion is stirred until homogeneous；Graphite is added to obtained by upper step
Mixture in, be stirred until homogeneous dispersion；SBR in the aqueous adhesive of lignin-base is added to the resulting mixture of upper step
In, it is stirred until homogeneous dispersion, obtains electrode slurry (solid content 55%)；Obtained electrode slurry is evenly applied to Cu foil
On, 100 DEG C of vacuum drying roll to get graphite negative electrode of lithium ion battery electrode slice.
2, interpretation of result:
Fig. 7 is the outside drawing after the coating of the present embodiment graphite cathode slurry is dry.It is apparent that when water-soluble lignin and
The mass ratio of SBR is 6:1, and the rear electrode material of rolling directly falls off from copper foil, shows that the toughness of electrode material is very poor (with figure
1 compares), battery assembly can not be carried out.
Comparative example 2
1, the preparation of electrode is tested:
The mass ratio of graphite, conductive black (Super P) and the aqueous adhesive of lignin-base is 85:6:9.Lignin-base water
The mass ratio of water-soluble lignin (binary mixture of calcium lignosulfonate and carboxylated alkali lignin) and SBR in property adhesive
For 1:14.Water-soluble lignin in the aqueous adhesive of lignin-base is added in appropriate deionization, stirring keeps it sufficiently molten
Solution；Conductive black is added in the resulting lignin aqueous solution of upper step, dispersion is stirred until homogeneous；Graphite is added to upper step institute
In the mixture obtained, it is stirred until homogeneous dispersion；SBR in the aqueous adhesive of lignin-base is added to the resulting mixture of upper step
In, it is stirred until homogeneous dispersion, obtains electrode slurry (solid content 50%)；Obtained electrode slurry is evenly applied to Cu foil
On, 100 DEG C of vacuum drying roll to get graphite negative electrode of lithium ion battery electrode slice.The pole piece cut-parts being dried in vacuo are weighed
Afterwards, it is assembled in 2032 battery cases in glove box, is to electrode, using polyethylene film as diaphragm, with 1M with lithium piece
LiPF6EC/DMC/DEC (v/v/v=1/1/1) is electrolyte assembled battery.
2, interpretation of result:
Fig. 8 is the present embodiment graphite cathode.It is apparent that when the mass ratio of water-soluble lignin and SBR are 1:14, battery
Charge migration resistance can greatly increase (compared with Fig. 3 result).
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (8)
1. a kind of aqueous adhesive of lignin-base for negative electrode of lithium ion battery, it is characterised in that including following parts by weight
Component:
100 parts of water-soluble lignin
20~1000 parts of butadiene-styrene rubber；
The water-soluble lignin includes lignosulfonates, sulfonated wheat-strew lignin, sulfonation enzymolysis xylogen, carboxyl choline wood
Quality, carboxylated enzymolysis xylogen, ammonium choline lignin, amination alkali lignin, amination enzymolysis xylogen and ammoniumization enzymatic hydrolysis are wooden
At least one of element.
2. a kind of lithium-ion electric based on the aqueous adhesive of the lignin-base for negative electrode of lithium ion battery described in claim 1
Pond negative electricity pole piece.
3. negative electrode of lithium ion battery electrode slice according to claim 2, it is characterised in that: the negative electrode of lithium ion battery electricity
It include active material, conductive agent and the lignin-base described in claim 1 for negative electrode of lithium ion battery in the component of pole piece
Aqueous adhesive.
4. negative electrode of lithium ion battery electrode slice according to claim 3, it is characterised in that: the negative electrode of lithium ion battery electricity
Active material, conductive agent and the described in any item lignin-base water for negative electrode of lithium ion battery of claims 1 to 3 in pole piece
Property adhesive mass ratio be (70~95): (1~20): (4~10).
5. a kind of preparation method of negative electrode of lithium ion battery electrode slice according to claim 4, it is characterised in that including with
Lower step:
It will be water-soluble in the described in any item aqueous adhesives of lignin-base for being used for negative electrode of lithium ion battery of claims 1 to 3
Property lignin, conductive agent, active material, the described in any item lignin-bases for negative electrode of lithium ion battery of claims 1 to 3
Butadiene-styrene rubber in aqueous adhesive sequentially adds in water, stirs evenly, and electrode slurry can be obtained, it is coated on Cu foil
On, it is dry, it rolls to get negative electrode of lithium ion battery electrode slice.
6. the preparation method of negative electrode of lithium ion battery electrode slice according to claim 5, it is characterised in that: the electrode slurry
The solid content of material is 30~70 wt%.
7. the preparation method of negative electrode of lithium ion battery electrode slice according to claim 6, it is characterised in that: the drying
Condition is that constant-temperature vacuum dries 12~48 h at 80~120 DEG C.
8. a kind of lithium ion battery containing the described in any item negative electrode of lithium ion battery electrode slices of claim 2~4.
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| CN107359352A (en) * | 2017-06-13 | 2017-11-17 | 中国科学技术大学 | A kind of negative electrode of lithium ion battery electrode slice and preparation method thereof and lithium ion battery |
| CN109301248B (en) * | 2017-07-24 | 2021-05-04 | 南方科技大学 | Battery negative plate, preparation method thereof and lithium ion battery |
| CN110061239B (en) * | 2018-03-20 | 2022-07-05 | 南方科技大学 | Lignin-based binder, preparation method thereof and lithium ion battery |
| EP3544099A1 (en) | 2018-03-21 | 2019-09-25 | Borregaard AS | Dispersant and binder for lithium ion batteries based on modified lignin and carboxymethyl cellulose |
| JP6819911B2 (en) * | 2019-02-08 | 2021-01-27 | トヨタ自動車株式会社 | Negative electrode for lithium ion secondary battery |
| CN110229275B (en) * | 2019-06-19 | 2021-11-05 | 江苏塔菲尔新能源科技股份有限公司 | Binder, preparation method thereof, pole piece containing binder and lithium ion battery |
| CN110752370A (en) * | 2019-10-29 | 2020-02-04 | 广州鹏辉能源科技股份有限公司 | Binder, positive electrode slurry, positive plate and lithium ion battery |
| CN111384424B (en) * | 2019-11-05 | 2021-10-19 | 郑州大学 | Lignin-based complex electrolyte for aqueous zinc-ion battery and aqueous zinc-ion battery based on same |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101350404A (en) * | 2008-09-04 | 2009-01-21 | 上海交通大学 | Lithium ion battery cathode and preparation method thereof |
| CN101475604A (en) * | 2009-01-23 | 2009-07-08 | 华南理工大学 | Method for preparing highly sulfonated sodium lignosulfonate |
| CN102174202A (en) * | 2011-03-18 | 2011-09-07 | 华南理工大学 | Water-soluble alkali lignin carboxylate and preparation method thereof |
| CN102733230A (en) * | 2012-07-05 | 2012-10-17 | 东北林业大学 | Process for producing high-purity ammonium lignin by taking papermaking black liquid as material |
| CN103483597A (en) * | 2013-08-26 | 2014-01-01 | 中国林业科学研究院林产化学工业研究所 | Method for modifying enzymatic hydrolysis lignin by alkali activation |
| CN104017520A (en) * | 2014-05-27 | 2014-09-03 | 中国科学院广州能源研究所 | Terpene resin based aqueous binder and application thereof to lithium ion battery cathode or super capacitor |
| CN104081568A (en) * | 2012-02-16 | 2014-10-01 | 株式会社Lg化学 | Lithium secondary battery having anode containing aqueous binder |
| CN104194002A (en) * | 2014-08-20 | 2014-12-10 | 华南理工大学 | High-sulfonation-degree lignosulfonate containing alkyl sulfonic acid, and preparation method and application thereof |
-
2016
- 2016-05-25 CN CN201610357495.2A patent/CN106025283B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101350404A (en) * | 2008-09-04 | 2009-01-21 | 上海交通大学 | Lithium ion battery cathode and preparation method thereof |
| CN101475604A (en) * | 2009-01-23 | 2009-07-08 | 华南理工大学 | Method for preparing highly sulfonated sodium lignosulfonate |
| CN102174202A (en) * | 2011-03-18 | 2011-09-07 | 华南理工大学 | Water-soluble alkali lignin carboxylate and preparation method thereof |
| CN104081568A (en) * | 2012-02-16 | 2014-10-01 | 株式会社Lg化学 | Lithium secondary battery having anode containing aqueous binder |
| CN102733230A (en) * | 2012-07-05 | 2012-10-17 | 东北林业大学 | Process for producing high-purity ammonium lignin by taking papermaking black liquid as material |
| CN103483597A (en) * | 2013-08-26 | 2014-01-01 | 中国林业科学研究院林产化学工业研究所 | Method for modifying enzymatic hydrolysis lignin by alkali activation |
| CN104017520A (en) * | 2014-05-27 | 2014-09-03 | 中国科学院广州能源研究所 | Terpene resin based aqueous binder and application thereof to lithium ion battery cathode or super capacitor |
| CN104194002A (en) * | 2014-08-20 | 2014-12-10 | 华南理工大学 | High-sulfonation-degree lignosulfonate containing alkyl sulfonic acid, and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| lignin as a Binder Material for Eco-Friendly Li-Ion Batteries;Huiran Lu et al;《materials》;20160225;第9卷(第3期);第1页至第4页第3段，Results and Discussion部分 |
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|---|---|
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