CN105895193A - Silver conductive coating material of lithium ion battery, preparation method of silver conductive coating material and lithium ion battery - Google Patents
Silver conductive coating material of lithium ion battery, preparation method of silver conductive coating material and lithium ion battery Download PDFInfo
- Publication number
- CN105895193A CN105895193A CN201610392713.6A CN201610392713A CN105895193A CN 105895193 A CN105895193 A CN 105895193A CN 201610392713 A CN201610392713 A CN 201610392713A CN 105895193 A CN105895193 A CN 105895193A
- Authority
- CN
- China
- Prior art keywords
- conductive coating
- conductive
- coating materials
- lithium ion
- weight portion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- 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
-
- 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
-
- 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 provides a silver conductive coating material of a lithium ion battery. The conductive coating material comprises the following constituents by weight: 100 parts of conductive agent, 20-150 parts of binding agent, 0-30 parts of polyvinylpyrrolidone and 500-10,000 parts of water, wherein on the basis of 100 parts of conductive agent, graphite flakes account for 10-100 parts, conductive carbon black accounts for 1-50 parts, and a carbon nanotube accounts for 0-80 parts. The invention also provides a preparation method of the above silver conductive coating material and the lithium ion battery employing the conductive coating material. In the conductive coating material, different types of conductive agents are creatively used, and the paste stability can be improved; meanwhile, due to a synergistic effect of various conductive agents, the dynamic internal resistance increase of a battery core also can be further reduced, and the rate performance of the battery is improved; and moreover, a pole plate shows silver after a base coat of the conductive coating material is coated, the base conductive coating can be continuously achieved, and the requirements of various intermittent coating structured pole plates in different sizes are met.
Description
Technical field
The present invention relates to field of lithium ion battery, the silver color conduction more particularly, to a kind of lithium ion battery is coated with
Layer material and preparation method thereof and a kind of lithium ion battery.
Background technology
Along with developing rapidly of field of batteries, people are more and more higher to the requirement of all kinds of power supplys, wherein lithium-ion electric
Pond is high with its voltage, lightweight, memory-less effect, have extended cycle life and many superioritys such as non-environmental-pollution
Can be widely used.Lithium ion battery, as a kind of electrochmical power source, specifically includes that battery container, is sealed in electricity
Pole piece in the housing of pond and nonaqueous electrolytic solution；Wherein, pole piece includes battery anode slice, negative plate and barrier film, institute
The positive plate stated, by positive plate active material and corresponding binding agent, dispersant, solvent mix and blend, forms slurry
Material, coating on a current collector and carries out drying, prepares after tabletting, including positive plate collector and be formed at positive pole
Active material layer on sheet collector, described positive plate collector typically uses aluminium foil；Described negative plate is by bearing
Pole piece active material and corresponding binding agent, dispersant, solvent mix and blend, form slurry, be coated in afflux
On body and carry out drying, prepare after tabletting, including negative plate collector and be formed at the work on negative plate collector
Property material layer, described negative plate collector typically uses Copper Foil.
At present, along with the development of new energy technology, the demand for lithium-ion-power cell is growing.Single
The shift in demand that uses of battery is the use demand of multi-series and parallel assembled battery, and traditional lithium ion battery is difficult to
Meet electrokinetic cell high concordance and the requirement of long life.Utilize conductive coating materials to the positive plate of battery,
Negative plate carries out surface process and to form functional coating be a breakthrough technological innovation, and carbon coated aluminum foil/Copper Foil is just
It is that scattered conductive nano graphite and carbon are coated with grain, is coated on aluminium foil/Copper Foil uniform, fine and smoothly.Its energy
Splendid static conductive performance is provided, collects micro-electric current of active material, such that it is able to positive/negative is greatly lowered
Contact resistance between sheet active material and collector, and adhesive ability between the two can be improved, can reduce viscous
The usage amount of knot agent, and then make the overall performance generation of battery be obviously improved.
But, the conductive coating that existing this conductive coating materials is formed is black, color and active material layer
Color very close to, intermittently during the film-making of cloth of coating-type structure pole piece, fiber sensor None-identified distinguish conductive coating and
Active material layer, so conductive coating needs to carry out batch (-type) primary coat according to pole piece size, (during primary coat, conduction is coated with
Layer longitudinally interval, discontinuously, intermediary position is empty paper tinsel.), production efficiency relative to continuous way primary coat (during primary coat,
Conductive coating is longitudinally continuous.) reduce the most.Further, existing conductive coating does not have weldability, it is impossible to
Carry out tab welding, so conductive coating needs for carrying out batch (-type) primary coat according to pole piece size, significantly drop
Low production efficiency.
Summary of the invention
Present invention seek to address that technical problem present in prior art, it is provided that one is remarkably improved lithium ion
The conductive coating materials of the silver color lithium ion battery of the chemical property of battery, and this conductive coating materials shape
The conductive coating become has weldability；And the preparation side of this silver color conductive coating materials is provided further
Method and use the lithium ion battery of this conductive coating materials.
First, the invention provides the silver color conductive coating materials of a kind of lithium ion battery, described conductive coating material
In material, each component is by weight, including: conductive agent 100 weight portion, binding agent 20～150 weight portion, poly-second
Alkene pyrrolidone 0～30 weight portion, water 500～10000 weight portion；Wherein, with the conductive agent of 100 weight portions it is
Benchmark, graphite flake 10～100 weight portion, conductive black 1～50 weight portion, CNT 0～80 weight portion.
Present invention also offers the preparation method of the conductive coating materials of above-mentioned lithium ion battery, comprise the steps: by
In conductive coating materials, conductive agent and polyvinylpyrrolidone are sequentially added into the moisture of binding agent by the ratio of each component
Dissipate in liquid, after stirring, more repeatedly grind and disperse, until being uniformly dispersed, to obtain described lithium ion battery
Conductive coating materials.
Invention further provides a kind of lithium ion battery, including: battery container, be sealed in battery container
Pole piece and nonaqueous electrolytic solution；Described pole piece includes battery anode slice, negative plate and barrier film；Described anode
Sheet, negative plate include: collector and be coated on the conductive coating materials on described collector, described conduction
Coating material selects conductive coating materials as above.
The present invention uses different types of conductive agent innovatively, including Graphene, conductive black and CNT
As conductive agent, can improve Stability of Slurry, the cooperative effect of the most multiple conductive agent can also drop further
Low battery core dynamic internal resistance amplification, and improve battery high rate performance, and pole piece after conductive coating materials coating primary coat
Outward appearance is silver color, it is possible to realize continuous primary coat conductive coating, meets various different size interval cloth of coating-type structure pole
The requirement of sheet.It addition, the conductive coating that the coating of this conductive coating materials is formed has weldability, it is possible to
Conductive coating position carries out tab welding, it is possible to be effectively improved production efficiency.Further, the lithium of the present invention is used
The lithium ion battery not only production efficiency that the silver color conductive coating materials of ion battery makes is high, cost-effective, and
And there is preferably chemical property, and including having low internal resistance, high magnification, long life and good high temperature
Performance.
Detailed description of the invention
Hereinafter the preferred embodiments of the present invention are illustrated, it will be appreciated that described herein be preferable to carry out
Example is merely to illustrate and explains the present invention, is not intended to limit the present invention.
The lithium ion battery of the preferred embodiment of the present invention, including battery container, the pole that is sealed in battery container
Core and nonaqueous electrolytic solution；Described pole piece includes battery anode slice, negative plate and barrier film.
Wherein, described negative plate is mixed by negative plate active material and corresponding binding agent, dispersant, solvent
Closing stirring, form slurry, coating on a current collector and carries out drying, prepares, including negative plate collection after tabletting
Fluid and be formed at the active material layer on negative plate collector.As the collector for negative plate, permissible
Being Copper Foil, stainless steel foil, nickel foil, shape can be mesh-like, foil-like.Described negative plate active material,
Binding agent, dispersant and solvent can use and well known to a person skilled in the art negative plate active material, glue
Knot agent, dispersant and solvent.
Described positive plate by positive plate active material and corresponding binding agent, dispersant, solvent mix and blend,
Forming slurry, coating on a current collector and carries out drying, prepares, including positive plate collector and shape after tabletting
Become the active material layer on positive plate collector.As the collector for positive plate, can be aluminium foil,
Stainless steel foil, shape can be mesh-like, foil-like.Described positive plate active material, binding agent, dispersant
And solvent can use well known to a person skilled in the art positive plate active material, binding agent, dispersant with
And solvent.
Described barrier film can be non-woven fabrics, synthetic resin microporous membrane；Preferential use synthetic resin microporous membrane,
Specifically there are polyethene microporous membrane, microporous polypropylene membrane, polyethylene polypropylene composite micro porous film, TPO micro-
Pore membranes etc., are preferred with polyolefin microporous film the most again.
Described electrolyte is non-aqueous electrolyte.To electrolyte therein, common non-aqueous solution electrolysis can be used
The electrolytic salt that liquid uses, such as LiPF6、LiBF4、LiAsF6、LiClO4、LiSbF6、LiCl、LiBr、
LiCF2SO3Deng lithium salts, consider from oxidation stability angle, preferably select LiPF6、LiClO4、LiBF4、
LiAsF6In one or more.Electrolyte solvent for use is organic solvent, can be those skilled in the art
Known electrolyte solvent.
The present invention is characterized by the collector of positive plate and/or negative plate, first one layer of conductive coating of coating
Material forms conductive coating, is coated with active material and forms active material layer；By described conductive coating, energy
Splendid static conductive performance is provided, collects micro-electric current of active material, such that it is able to be greatly lowered positive/negative
Contact resistance between pole piece active material and collector, and adhesive ability between the two can be improved, can subtract
The usage amount of few binding agent, and then make the overall performance generation of battery be obviously improved.
It will be apparent to one skilled in the art that the conductive coating that existing this conductive coating materials is formed is black,
Color and active material layer color very close to, intermittently during the film-making of cloth of coating-type structure pole piece, fiber sensor cannot
Identify and distinguish conductive coating and active material layer, so conductive coating needs to carry out batch (-type) according to pole piece size
Primary coat, production efficiency reduces the most relative to continuous primary coat.Further, do not have can for existing conductive coating
Weldability, it is impossible to carry out tab welding, so conductive coating needs for carrying out batch (-type) according to pole piece size
Primary coat, is greatly lowered production efficiency.Thus, present inventor is through long-term research, it is proposed that
Technical scheme, using the teaching of the invention it is possible to provide the silver color of a kind of chemical property being remarkably improved lithium ion battery
The conductive coating materials of lithium ion battery, and this conductive coating materials formed conductive coating have solderable
Connecing property.
The conductive coating materials of the lithium ion battery of the present invention, by each component by weight, including: conduction
Agent 100 weight portion, binding agent 20～150 weight portion, polyvinylpyrrolidone 0～30 weight portion, water
500～10000 weight portions；Wherein, on the basis of the conductive agent of 100 weight portions, graphite flake 10～100 weight
Part, conductive black 1～50 weight portion, CNT 0～80 weight portion.
It is noted that described binding agent, using polyacrylate dispersion, solid content is 1～50%, can
Realizing the goal of the invention of the present invention, in the preferred case, its solid content is 20～30%.The present invention utilizes poly-third
Olefin(e) acid ester emulsion is as the sagging inhibitor of conductive coating and binding agent, and it has the chemical stability of excellence, network
Conjunction property and surface activity, as a kind of colloid, can improve Graphene, conductive black and CNT and lead
Dispersibility in plasma-based material.Simultaneously as the binding agent between conductive agent powder body and between conductive agent and collector, rise
Good adhesive property, it is ensured that the high-peeling strength of conductive coating.In situations where it is preferred, polyacrylate
Emulsion is 70～90 weight portions, after chelating so that Graphene, conductive black and CNT are in conduction
Dispersibility in slurry more preferably, and makes the adhesive property between conductive agent powder body and between conductive agent and collector
More preferably, it is ensured that the high-peeling strength of conductive coating.Described binding agent may be used without sanlose and
Butadiene-styrene rubber mixed solution, the aqueous dispersions (such as LA133) of acrylonitrile multiple copolymer and Shandong Shan chemical industry
6012 or 6016, solid content is 1～50%, and in the preferred case, its solid content is 20～30%, is water
It is binding agent, as a kind of colloid, graphite flake, conductive black and CNT can be significantly improved in conduction
Dispersibility in slurry.Simultaneously as the binding agent between conductive agent powder body and between conductive agent and collector, it is possible to
Play good adhesive property, it is ensured that the high-peeling strength of conductive coating.
The present invention utilizes nontoxic, amphiphilic water-soluble macromolecular material polyvinylpyrrolidone to be as conductive coating
Dispersant, it can dissolve each other with multiple macromolecule, lower-molecular substance or compound, has the chemically stable of excellence
Property, biocompatibility, complexing and surface activity, as a kind of high molecular surfactant, can improve
Graphene, conductive black and the CNT dispersibility in electrocondution slurry.Dissolve each other with binding agent and multiple simultaneously
Close, improve the stability of electrocondution slurry further.In the preferred case, polyvinylpyrrolidone is 5～15 weights
Amount part, it is possible to preferably improve conductive agent dispersibility in electrocondution slurry, and preferably improve conductive paste
The stability of material.
The present invention utilizes graphite flake, conductive black and CNT as the conductive agent of conductive coating, and three kinds are not
With the conductive agent of size, can realize multi-level filling and connect effect, conductive black is little of conductive nano
Grain, CNT is tubular structure, and graphite flake is Nano grade laminated structure, by the association of multiple conductive agent
Adjust effect, the three-dimensional conductive network in " point-line-face " can be formed, greatly strengthen the stability of conductive network and lead
The sustainability that electric pathway builds.Meanwhile, graphite flake and CNT, pattern becomes silver color, with graphite
Sheet and CNT are main conductive agent, thus make silver color conductive coating.In the preferred case, lead described in
In coating material, each component is by weight, including: graphite flake 50～80 weight portion, conductive black 20～40
Weight portion, CNT 5～15 weight portion, water 1700～2000 weight portion.Use leading of above-mentioned preferred ingredient
Electricity agent has preferably conducts electricity coordinative role, and conductive coating outward appearance and active material layer have and preferably may be used simultaneously
Identity.
Wherein, graphite flake is small Multi-layer graphite, when the number of plies is less than 10 layers, and referred to as multi-layer graphene, and stone
Ink alkene is the new material of a kind of monolayer laminated structure being made up of carbon atom, be a kind of by carbon atom with sp2 hydridization
Track composition hexangle type is the flat film of honeycomb lattice, the two-dimensional material of only one of which carbon atom thickness.?
Under preferable case, the particle mean size of described graphite flake is less than 500nm, the preferred average particle size stone less than 5nm
Ink alkene, the more preferably particle mean size Graphene less than 2nm.Use the Graphene of above-mentioned particle diameter and size, make
Obtain the filling effect between conductive agent more preferable, can further improve the electric conductivity of conductive coating.
CNT as monodimension nanometer material, be one have special construction (radial dimension is nanometer scale,
Axial dimension is micron dimension, and pipe two ends are substantially all sealing) One-dimensional Quantum material.CNT is main
The coaxial pipe of several layers to tens of layers it is made up of the carbon atom of hexagonal arrangement.Keep fixing between layers
Distance, about 0.34nm.CNT caliber is 1～5nm, a length of 10～20 μm.Carbon in CNT
Atom is hybridized to main with sp2, and hexangle type network exists a certain degree of bending simultaneously, forms space and opens up
Flutterring structure, wherein can form certain sp3 hybrid bond, the chemical bond i.e. formed has sp2 and sp3 simultaneously
Mixed hybridization state, and these p tracks overlap each other and form height delocalization outside CNT graphene sheet layer
The big π key changed, the big π key of CNT outer surface is that CNT has big point of conjugation performance with some
The chemical fundamentals that son is combined with non-covalent bond.
The particle mean size of described conductive black is 10～60nm, preferably 10～40nm.The pipe of described CNT
Footpath is 1～5nm, and a length of 0.1～20 μm, preferably caliber are 1～2nm, a length of 10～20 μm.In employing
Stating particle diameter and the conductive black of size and CNT, the filling effect between conductive agent is more preferable, can be further
Improve the electric conductivity of conductive coating.Described conductive black can use common conductive black Super-P, excellent
Choosing uses Ketjen black, it is only necessary to extremely low addition just can reach high conductivity.
Described water can select deionized water, distilled water, pure water etc., it is preferred to use deionized water.Use
Deionized water can exclusive segment ion interference, parameter is controlled；In situations where it is preferred, water is 1700～2000
Weight portion.
In situations where it is preferred, described conductive coating materials also includes defoamer, 0.1～3 of 0.1～5 weight portions
The preservative of weight portion.Described defoamer and described preservative can use defoamer well known in the art and prevent
Rotten agent, its effect is the most known to those skilled in the art.Preferably, described defoamer is selected from ethanol, positive fourth
One or more in alcohol；Described preservative is selected from phenol, cresol, chlorocresol, thymol, oxybenzene ester
Class, benzoic acid and its esters, sorbic acid and salt thereof, boric acid and its esters, propanoic acid, dehydroacetic acid, formaldehyde,
One or more in glutaraldehyde.Use these preferred defoamer and preservative can improve conductive coating materials
Processing procedure and storage performance.
The preparation method of the conductive coating materials of above-mentioned lithium ion battery comprises the steps: to be coated with by above-mentioned conduction
In layer material, conductive agent and polyvinylpyrrolidone are sequentially added into acrylonitrile multiple copolymer by the ratio of each component
Aqueous dispersions in, after stirring, more repeatedly grind and disperse, until being uniformly dispersed, to obtain described lithium
The conductive coating materials of ion battery.
In situations where it is preferred, described preparation method also includes adding in binding agent by chelating agen, stirring chelating
After disperse in water, then in the ratio of component each in conductive coating materials by conductive agent and polyvinylpyrrolidone
It is sequentially added into, adds defoamer and preservative further, after stirring, more repeatedly grind and disperse straight
To being uniformly dispersed, obtain the conductive coating materials of described lithium ion battery.
In the present invention, described stirring can realize in existing blender, and the linear velocity of stirring is
10～30m/s, mixing time is 1～5 hour；Described grinding and dispersion can use ball mill or high speed dispersion
Machine is carried out；The zirconium pearl selection of dimension 0.5～1.0mm that described ball mill uses, in described dispersive process, slurry temperature
Degree controls below 40 DEG C.Described blender, ball mill and high speed dispersor can use people in the art
Blender, ball mill and the high speed dispersor that member is commonly used.Stirring and ball milling use the most above-mentioned parameter,
Dispersion effect between conductive agent and conductive agent and other component more preferably, conductive coating slurry particle diameter after dispersion
Less than 0.5 μm.
The manufacture method of the lithium ion battery of the present invention is the manufacture method of conventional lithium ion battery, by inciting somebody to action
Above-mentioned prepared positive plate and negative plate and barrier film use takeup type or stacked constitute pole piece, then should
Pole piece is put in battery case, welding block, fluid injection, seal, be melted into after prepare lithium ion battery.Difference
It is, when the making of positive plate and negative plate, is first coated with conductive coating on a current collector.
Thus, present invention also offers a kind of lithium ion battery, including: battery container, be sealed in battery case
Internal pole piece and nonaqueous electrolytic solution；Described pole piece includes battery anode slice, negative plate and barrier film；Described electricity
Pond positive plate and/or negative plate include: collector and be coated on the conductive coating on described collector, institute
State after conductive coating uses conductive coating materials as above coating and obtain.Described painting method can use
The painting method of existing active material, does not repeats at this.This lithium ion battery is compared to existing lithium
Ion battery, has more preferably chemical property, including having low internal resistance, high magnification, the long life and
Good high-temperature behavior.
The following example can be more conducive to the present invention is described, it should be appreciated that these embodiments are to enter the present invention
One step is explained and explanation, does not constitutes any limitation the present invention.
Embodiment 1～7
(1) calcium hydroxide is added shown in table 1 by component and content according to the conductive coating materials in table 1
In binding agent, stir 24 hours and disperse in water after chelating, then press the component of conductive coating materials in table 1
With in the aqueous dispersions that conductive agent and polyvinylpyrrolidone are sequentially added into the binding agent after chelating by content, stir
After mixing 1 hour (wherein, described stirring linear velocity is 20m/s), then through ball mill grinding 5 times until dividing
Dissipate uniformly, obtain the silver color conductive coating materials of the lithium ion battery of embodiment 1～5.
(2) according to existing lithium ion battery manufacture method, make lithium ion battery, difference be lithium from
One layer of silver color conductive coating materials is first coated on the positive plate of sub-battery and negative plate collector；Obtain embodiment
The lithium ion battery of 1～5.
The preparation method of embodiment 6,7 and the difference of embodiment 5 are that binding agent carries out chela without chelating agen
Close, according to the component of the conductive coating materials in table 1 and content by conductive agent and polyvinylpyrrolidone successively
Add in the aqueous dispersions of binding agent, after stirring, more repeatedly grind and disperse until being uniformly dispersed,
Conductive coating materials to the lithium ion battery of embodiment 6,7.
Comparative example 1
Uncoated conductive coating materials on the lithium ion battery of comparative example 1, its positive plate and negative plate collector.
Comparative example 2
The lithium ion battery of comparative example 2, on its positive pole and negative current collector, coating is as described in background technology
Scattered conductive nano graphite and carbon cladding grain.
Comparative example 3
The lithium ion battery of comparative example 3, conductive agent is provided without conductive black, uses CNT and graphite flake.
Comparative example 4
The lithium ion battery of comparative example 4, is provided without graphite flake in its component, use CNT and conduction charcoal
Black.
Comparative example 5
The lithium ion battery of comparative example 5, is provided without polyacrylate dispersion as binding agent in its component, and
It is to use existing Kynoar as dispersant.Solvent deionized water changes to N-Methyl pyrrolidone.
Performance test
By the embodiment of the present invention 1～5 and the lithium ion battery for preparing of comparative example 1～5 carry out following performance test.
1C multiplying power discharging cycle performance and inner walkway: lithium prepared by embodiment 1-5 and comparative example 1～5 from
After sub-Battery formation, partial volume, respectively take 20 batteries, hold up a day BS-9365 secondary cell device for detecting performance
On, test 55 DEG C of 1C and circulate 500 capability retentions.Step is as follows: shelve 10min；Charge with 1C
To 3.8V/0.05C；Shelve 10min；With 1C constant-current discharge to 2.0V, it is 1 circulation.Repetitive cycling
Number of times 500 times, records the capability retention after 500 times and internal resistance, and often group is averaged.
Capacity test method: after the lithium ion battery chemical conversion of embodiment 1-5 and comparative example 1～5 preparation, partial volume,
Respectively taking 20 batteries, holding up on day BS-9365 secondary cell device for detecting performance, test different multiplying gram is held
Amount.Step is as follows: shelve 10min；3.8V/0.05C is charged to 1C；Shelve 10min；With 1C constant current
Being discharged to 2.0V, recording capacity numerical value, except in corresponding positive plate LiFePO4 weight, obtaining corresponding battery gram
Capacity, often group is averaged.Then 10min is shelved；3.8V/0.05C is charged to 1C；Shelve 10min；
With 3C constant-current discharge to 2.0V, recording capacity numerical value, except in corresponding positive plate LiFePO4 weight, it is right to obtain
Answering battery gram volume, often group is averaged.Shelve 10min；3.8V/0.05C is charged to 1C；Shelve 10min；
With 5C constant-current discharge to 2.0V, recording capacity numerical value, except in corresponding positive plate LiFePO4 weight, it is right to obtain
Answering battery gram volume, often group is averaged.
Welding effect method of testing: take width 6mm, thickness 0.1mm lug, is welded on 15 μm aluminium foil tables
Face.Use to win and close YEW150D-B pelleter, bonding power 20%, welding pressure 0.1Mpa, super weldering time
0.5S. nugget length 15mm, width 4mm.Shanghai enterprise is used to think that instrument QX-W400 type measurer for pulling force is surveyed
Examination tab welding pulling force.Welding pulling force is more than 20N, and definition welding effect is good；Pulling force between 10 to 20N,
Definition welding effect is general, and pulling force is less than 10N, and definition welding effect is poor.
How fiber amplifier identifies: taking use and win conjunction YEW150D-B pelleter, sensing pole piece carries out pole
Ear welds.Optical fiber head distance pole piece 2-5mm.All pole pieces have all welded lug, are defined as can recognize that；
As long as there being the unwelded lug of pole piece, it is defined as not can recognize that.
Above test result is as shown in table 2:
Table 2-1
Table 2-2
It can be seen that use the lithium that the preparation method of embodiment of the present invention 1-5 prepares from table 2-1, table 2-2
Ion battery, compared to using the lithium ion battery prepared of comparative example 1-5, have preferable capability retention,
Cycle performance, internal resistance performance are with welding performance, and fiber amplifier is capable of identify that conductive coating and active matter
Matter layer.And in embodiment 1-7, embodiment 1 uses preferred component and content, embodiment 2 to be not added with
CNT, the content of the binding agent of embodiment 3 is not in the range of preferably, and embodiment 4 is not added with polyethylene
Ketopyrrolidine, the content of the constituent part of embodiment 4,5 not in the range of preferably, embodiment 6,7 viscous
Knot agent may know that without chelating, comparative example 1-7, uses preferred ingredient and content, and through chelating agen
Process the lithium ion battery made by conductive coating materials chemical property more preferably, including having more preferably
Capability retention, cycle performance, internal resistance performance are with welding performance, and fiber amplifier is capable of identify that conduction
Coating and active material layer.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all at this
Any amendment, equivalent and the improvement etc. made within bright spirit and principle, should be included in the present invention
Protection domain within.
Claims (10)
1. the silver color conductive coating materials of a lithium ion battery, it is characterised in that in described conductive coating materials
Each component by weight, including conductive agent 100 weight portion, binding agent 20～150 weight portion, polyethylene pyrrole
Pyrrolidone 0～30 weight portion, water 500～10000 weight portion；Wherein, on the basis of the conductive agent of 100 weight portions,
Graphite flake 10～100 weight portion, conductive black 1～50 weight portion, CNT 0～80 weight portion.
Conductive coating materials the most according to claim 1, it is characterised in that described conductive coating materials is also
Chelating agen, 0.1～5 defoamer, 0.1～3 preservative of weight portion of weight portion including 0.1～5 weight portions.
Conductive coating materials the most according to claim 1, it is characterised in that in described conductive coating materials
Each component by weight, graphite flake 50～80 weight portion, conductive black 20～40 weight portion, CNT 5～15
Weight portion, binding agent 70～90 weight portion, polyvinylpyrrolidone 5～15 weight portion, water 1700～2000 weight
Part.
Conductive coating materials the most according to claim 1, it is characterised in that described conductive black average
Granularity is 10～60nm；The particle mean size of described graphite flake is less than 500nm；The caliber of described CNT is
1～5nm, a length of 0.1～20 μm.
Conductive coating materials the most according to claim 1, it is characterised in that described graphite flake is selected from average
The granularity single or multiple lift Graphene less than 5nm.
Conductive coating materials the most according to claim 1 and 2, it is characterised in that described binding agent is selected from
Polyacrylate dispersion, sanlose and butadiene-styrene rubber mixed solution, acrylonitrile multiple copolymer
One or more in aqueous dispersions, solid content is 1～50%；In described binding agent, add chelating agen carry out chela
Closing, described chelating agen selects one or more in calcium hydroxide, ammonia, potassium hydroxide and sodium hydroxide.
Conductive coating materials the most according to claim 2, it is characterised in that described defoamer selection ethanol,
One or more in n-butyl alcohol；Described preservative is selected from phenol, cresol, chlorocresol, thymol, oxybenzene
Esters, benzoic acid and its esters, sorbic acid and salt thereof, boric acid and its esters, propanoic acid, dehydroacetic acid, formaldehyde,
One or more in glutaraldehyde.
8. the silver color conductive coating materials of the lithium ion battery prepared as according to any one of right 1 to 7
Method, it is characterised in that comprise the steps: the ratio in component each in conductive coating materials by conductive agent and
Polyvinylpyrrolidone is sequentially added in the aqueous dispersions of binding agent, after stirring, more repeatedly grinds and disperses
Until being uniformly dispersed, obtain the conductive coating materials of described lithium ion battery.
Preparation method the most according to claim 8, it is characterised in that described preparation method also includes chela
Mixture adds in binding agent, disperses after stirring chelating in water, then the ratio in component each in conductive coating materials
Conductive agent and polyvinylpyrrolidone are sequentially added into, add defoamer and preservative further, after stirring,
The most repeatedly grind and disperse, until being uniformly dispersed, to obtain the conductive coating materials of described lithium ion battery；
Wherein, the linear velocity of described stirring is 10～30m/s, and mixing time is 1～24 hour；Described grinding and dispersion are adopted
Carry out with ball mill or high speed dispersor.The zirconium pearl selection of dimension 0.5～1.0mm that described ball mill uses, described point
During Saning, slurry temperature controls below 40 DEG C.
10. a lithium ion battery, including: battery container, the pole piece being sealed in battery container and non-water power
Solve liquid；Described pole piece includes battery anode slice, negative plate and barrier film；It is characterized in that, described battery anode slice
And/or negative plate includes: collector and be coated on the conductive coating on described collector, it is characterised in that
Described conductive coating obtains after using the conductive coating materials coating as described in any one of claim 1～7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610392713.6A CN105895193A (en) | 2016-06-05 | 2016-06-05 | Silver conductive coating material of lithium ion battery, preparation method of silver conductive coating material and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610392713.6A CN105895193A (en) | 2016-06-05 | 2016-06-05 | Silver conductive coating material of lithium ion battery, preparation method of silver conductive coating material and lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105895193A true CN105895193A (en) | 2016-08-24 |
Family
ID=56709850
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610392713.6A Pending CN105895193A (en) | 2016-06-05 | 2016-06-05 | Silver conductive coating material of lithium ion battery, preparation method of silver conductive coating material and lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105895193A (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106784857A (en) * | 2017-01-06 | 2017-05-31 | 深圳市德方纳米科技股份有限公司 | A kind of lithium ion battery water system primary coat collector and its preparation method and application |
| CN106848324A (en) * | 2017-01-06 | 2017-06-13 | 深圳市德方纳米科技股份有限公司 | A kind of lithium ion battery oiliness primary coat collector and its preparation method and application |
| CN107331439A (en) * | 2017-06-16 | 2017-11-07 | 清华大学 | CNT/nitrogen doped carbon nanotube nano graphite flakes electrocondution slurry and preparation method |
| CN107611448A (en) * | 2017-09-07 | 2018-01-19 | 湖北金泉新材料有限责任公司 | A kind of novel electrode and the lithium ion battery comprising the electrode |
| CN107749488A (en) * | 2016-11-28 | 2018-03-02 | 万向二三股份公司 | A kind of lithium battery of water system positive pole and preparation method thereof |
| CN108300056A (en) * | 2017-08-02 | 2018-07-20 | 天津市捷威动力工业有限公司 | A kind of cathode pole piece of lithium ion secondary battery primary coat coating |
| CN108365227A (en) * | 2018-04-20 | 2018-08-03 | 福建猛狮新能源科技有限公司 | A kind of various dimensions conduction composite current collector and its manufacturing method |
| CN108922653A (en) * | 2018-06-30 | 2018-11-30 | 中国科学院上海硅酸盐研究所 | A kind of perovskite carbon pastes used for solar batteries and electrode |
| CN109888295A (en) * | 2019-02-28 | 2019-06-14 | 合肥国轩高科动力能源有限公司 | A kind of affluxion body in lithium ion batteries coating paste, collector and preparation method thereof |
| CN110670057A (en) * | 2019-09-03 | 2020-01-10 | 河南豫清新能源产业有限公司 | Surface pretreatment method for copper foil of lithium battery |
| WO2020134648A1 (en) * | 2018-12-29 | 2020-07-02 | 宁德时代新能源科技股份有限公司 | Electrode plate, electrochemical device, battery module, battery pack, and equipment |
| CN111431498A (en) * | 2020-03-31 | 2020-07-17 | 中国科学院宁波材料技术与工程研究所 | Conductive polymer solution for crystal resonator and application thereof |
| CN113248989A (en) * | 2021-05-13 | 2021-08-13 | 湖北亿纬动力有限公司 | Conductive coating slurry and preparation method and application thereof |
| CN113745511A (en) * | 2020-05-29 | 2021-12-03 | 广州汽车集团股份有限公司 | Conductive slurry, preparation method of conductive slurry, negative current collector, negative plate, lithium ion battery cell, lithium ion battery pack and application of negative current collector, negative plate, lithium ion battery cell and lithium ion battery pack |
| CN113948710A (en) * | 2021-10-22 | 2022-01-18 | 珠海冠宇电池股份有限公司 | Positive current collector, positive plate and lithium ion battery |
| CN114023969A (en) * | 2021-11-03 | 2022-02-08 | 合肥国轩高科动力能源有限公司 | 3D creeper-type high-performance conductive agent and preparation method and application thereof |
| CN116410650A (en) * | 2021-12-29 | 2023-07-11 | 湖州欧美化学有限公司 | Thermosetting coating, preparation method of thermosetting coating and thermosetting coating |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102945945A (en) * | 2012-11-16 | 2013-02-27 | 双登集团股份有限公司 | Production method for pole piece of lithium ion battery |
| CN103268942A (en) * | 2013-03-19 | 2013-08-28 | 王樑 | Modified current collector with nano graphite coating |
| CN103779612A (en) * | 2013-12-19 | 2014-05-07 | 宁波维科电池股份有限公司 | Preparation method of flexibly packaged lithium ion power battery |
| CN104521045A (en) * | 2012-09-28 | 2015-04-15 | 日本瑞翁株式会社 | Conductive adhesive composition for electrochemical element electrode, collector with adhesive layer, and electrode for electrochemical element |
| CN104577130A (en) * | 2014-12-13 | 2015-04-29 | 山东神工海特电子科技有限公司 | Flexible-packaged high-power lithium iron phosphate power battery |
| CN104600320A (en) * | 2013-10-30 | 2015-05-06 | 上海悦达墨特瑞新材料科技有限公司 | Functional copper foil based on graphene and preparation method thereof |
-
2016
- 2016-06-05 CN CN201610392713.6A patent/CN105895193A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104521045A (en) * | 2012-09-28 | 2015-04-15 | 日本瑞翁株式会社 | Conductive adhesive composition for electrochemical element electrode, collector with adhesive layer, and electrode for electrochemical element |
| CN102945945A (en) * | 2012-11-16 | 2013-02-27 | 双登集团股份有限公司 | Production method for pole piece of lithium ion battery |
| CN103268942A (en) * | 2013-03-19 | 2013-08-28 | 王樑 | Modified current collector with nano graphite coating |
| CN104600320A (en) * | 2013-10-30 | 2015-05-06 | 上海悦达墨特瑞新材料科技有限公司 | Functional copper foil based on graphene and preparation method thereof |
| CN103779612A (en) * | 2013-12-19 | 2014-05-07 | 宁波维科电池股份有限公司 | Preparation method of flexibly packaged lithium ion power battery |
| CN104577130A (en) * | 2014-12-13 | 2015-04-29 | 山东神工海特电子科技有限公司 | Flexible-packaged high-power lithium iron phosphate power battery |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107749488A (en) * | 2016-11-28 | 2018-03-02 | 万向二三股份公司 | A kind of lithium battery of water system positive pole and preparation method thereof |
| CN106784857A (en) * | 2017-01-06 | 2017-05-31 | 深圳市德方纳米科技股份有限公司 | A kind of lithium ion battery water system primary coat collector and its preparation method and application |
| CN106848324A (en) * | 2017-01-06 | 2017-06-13 | 深圳市德方纳米科技股份有限公司 | A kind of lithium ion battery oiliness primary coat collector and its preparation method and application |
| CN106784857B (en) * | 2017-01-06 | 2020-04-07 | 深圳市德方纳米科技股份有限公司 | Water-based undercoat current collector for lithium ion battery and preparation method and application thereof |
| CN107331439A (en) * | 2017-06-16 | 2017-11-07 | 清华大学 | CNT/nitrogen doped carbon nanotube nano graphite flakes electrocondution slurry and preparation method |
| CN108300056A (en) * | 2017-08-02 | 2018-07-20 | 天津市捷威动力工业有限公司 | A kind of cathode pole piece of lithium ion secondary battery primary coat coating |
| CN107611448A (en) * | 2017-09-07 | 2018-01-19 | 湖北金泉新材料有限责任公司 | A kind of novel electrode and the lithium ion battery comprising the electrode |
| CN108365227A (en) * | 2018-04-20 | 2018-08-03 | 福建猛狮新能源科技有限公司 | A kind of various dimensions conduction composite current collector and its manufacturing method |
| CN108922653B (en) * | 2018-06-30 | 2020-08-14 | 中国科学院上海硅酸盐研究所 | Carbon slurry for perovskite solar cell and electrode |
| CN108922653A (en) * | 2018-06-30 | 2018-11-30 | 中国科学院上海硅酸盐研究所 | A kind of perovskite carbon pastes used for solar batteries and electrode |
| WO2020134648A1 (en) * | 2018-12-29 | 2020-07-02 | 宁德时代新能源科技股份有限公司 | Electrode plate, electrochemical device, battery module, battery pack, and equipment |
| CN109888295A (en) * | 2019-02-28 | 2019-06-14 | 合肥国轩高科动力能源有限公司 | A kind of affluxion body in lithium ion batteries coating paste, collector and preparation method thereof |
| CN109888295B (en) * | 2019-02-28 | 2021-09-03 | 合肥国轩高科动力能源有限公司 | Coating slurry for lithium ion battery current collector, current collector and preparation method of current collector |
| CN110670057A (en) * | 2019-09-03 | 2020-01-10 | 河南豫清新能源产业有限公司 | Surface pretreatment method for copper foil of lithium battery |
| CN111431498A (en) * | 2020-03-31 | 2020-07-17 | 中国科学院宁波材料技术与工程研究所 | Conductive polymer solution for crystal resonator and application thereof |
| CN111431498B (en) * | 2020-03-31 | 2023-09-01 | 中国科学院宁波材料技术与工程研究所 | Conductive polymer solution for crystal resonator and application thereof |
| CN113745511A (en) * | 2020-05-29 | 2021-12-03 | 广州汽车集团股份有限公司 | Conductive slurry, preparation method of conductive slurry, negative current collector, negative plate, lithium ion battery cell, lithium ion battery pack and application of negative current collector, negative plate, lithium ion battery cell and lithium ion battery pack |
| CN113248989A (en) * | 2021-05-13 | 2021-08-13 | 湖北亿纬动力有限公司 | Conductive coating slurry and preparation method and application thereof |
| CN113948710A (en) * | 2021-10-22 | 2022-01-18 | 珠海冠宇电池股份有限公司 | Positive current collector, positive plate and lithium ion battery |
| CN114023969A (en) * | 2021-11-03 | 2022-02-08 | 合肥国轩高科动力能源有限公司 | 3D creeper-type high-performance conductive agent and preparation method and application thereof |
| CN116410650A (en) * | 2021-12-29 | 2023-07-11 | 湖州欧美化学有限公司 | Thermosetting coating, preparation method of thermosetting coating and thermosetting coating |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105895193A (en) | Silver conductive coating material of lithium ion battery, preparation method of silver conductive coating material and lithium ion battery | |
| CN106047015A (en) | Conductive coating material for lithium ion battery, preparation method of conductive coating material and lithium ion battery | |
| Suriyakumar et al. | Mitigation of polysulfide shuttling by interlayer/permselective separators in lithium–sulfur batteries | |
| Chen et al. | Electrocatalytic NiCo2O4 nanofiber arrays on carbon cloth for flexible and high-loading lithium–sulfur batteries | |
| JP6017432B2 (en) | Slurry composition for forming lithium secondary battery electrode containing cellulose fiber as binder and electrode for lithium secondary battery | |
| Nie et al. | Biofilm nanofiber-coated separators for dendrite-free lithium metal anode and ultrahigh-rate lithium batteries | |
| Wu et al. | Electrocatalytic performances of g-C3N4-LaNiO3 composite as bi-functional catalysts for lithium-oxygen batteries | |
| Komaba et al. | Functional binders for reversible lithium intercalation into graphite in propylene carbonate and ionic liquid media | |
| Zhong et al. | The polyacrylic latex: an efficient water-soluble binder for LiNi 1/3 Co 1/3 Mn 1/3 O 2 cathode in li-ion batteries | |
| Kong et al. | Monodispersed MnOx-CeO2 solid solution as superior electrocatalyst for Li2S precipitation and conversion | |
| CN108258249A (en) | A kind of current collector coatings, slurry and preparation method thereof, battery pole piece and lithium ion battery | |
| JP7049004B2 (en) | Layered high capacity electrode | |
| CN102185126B (en) | The process for dispersing of microscale-nanoscale electrode material | |
| CN107615525A (en) | Cathode active material for secondary battery, the anode of secondary cell and secondary cell for including it | |
| CN102237521A (en) | Lithium ion battery anode slurry, anode and battery | |
| CN106229474A (en) | The multi-functional coatings of a kind of lithium ion battery and slurry and preparation method thereof and a kind of lithium ion battery | |
| CN109904394A (en) | Negative electrode material, preparation method thereof and secondary battery | |
| Shrshr et al. | Modified separator engineering with 2D ultrathin Ni3B@ rGO: Extraordinary electrochemical performance of the lithium-sulfur battery with enormous-sulfur-content cathode in low electrolyte/sulfur ratio | |
| CN102295898A (en) | Configuration and coating method of aluminium foil precoat nano conductive carbon primary coat liquid | |
| Ma et al. | Ultrafine NbN nanoparticle decorated nitrogen-doped carbon nanosheets with efficient polysulfide catalytic conversion for superior Li–S batteries | |
| Benehkohal et al. | Enabling green fabrication of Li-ion battery electrodes by electrophoretic deposition: growth of thick binder-free mesoporous TiO2-carbon anode films | |
| Huo et al. | Construction of advanced 3D Co3S4@ PPy nanowire anchored on nickel foam for high-performance electrochemical energy storage | |
| Wang et al. | Designing long-term cycle life for a lithium–air battery with a modified gas diffusion layer in terms of the moisture intrusion and electrolyte volatilization | |
| Sun et al. | Cerium oxysulfide with O–Ce–S bindings for efficient adsorption and conversion of lithium polysulfide in Li–S batteries | |
| Chen et al. | A Protein‐Based Janus Separator for Trapping Polysulfides and Regulating Ion Transport in Lithium− Sulfur Batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20171228 Address after: 518000 Guangdong Shenzhen city Longgang District Pingdi silver platform high technology Applicant after: Shenzhen Yu Qiang new materials Co. Ltd. Address before: 518000 Longgang District, Shenzhen City, Guangdong Province, 5-3-2703 Applicant before: Li Ke |
|
| TA01 | Transfer of patent application right | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160824 |
|
| RJ01 | Rejection of invention patent application after publication |