CN110176623A - A kind of preparation method of lithium ion battery - Google Patents
A kind of preparation method of lithium ion battery Download PDFInfo
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- CN110176623A CN110176623A CN201910497125.2A CN201910497125A CN110176623A CN 110176623 A CN110176623 A CN 110176623A CN 201910497125 A CN201910497125 A CN 201910497125A CN 110176623 A CN110176623 A CN 110176623A
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- lithium ion
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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
- H01M10/058—Construction or 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
- H01M4/625—Carbon or graphite
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a kind of preparation methods of lithium ion battery, the following steps are included: 1) be mixedly configured into anode sizing agent by positive active material, containing CNT (carbon nanotube) electrocondution slurry, binder and solvent, the anode sizing agent is coated on plus plate current-collecting body, anode pole piece is obtained；2) it is mixedly configured into negative electrode slurry by negative electrode active material, containing CNT (carbon nanotube) electrocondution slurry, binder and solvent, the negative electrode slurry is coated on negative current collector, cathode pole piece is obtained；3) lithium ion battery is assembled using the anode pole piece, the cathode pole piece, diaphragm and electrolyte.The preparation method of lithium ion battery provided by the invention is set about from battery pole piece electric conductivity is improved, and is added the conductive agent containing CNT into pole piece, is improved the active material ratio of battery pole piece itself.This method is generally applicable to various battery material systems, and makes simple, it is easy to accomplish large-scale industrial production.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular, to a kind of preparation method of lithium ion battery.
Background technique
Lithium ion secondary battery is as a kind of novel high-energy secondary power supply, big, discharging voltage balance, voltage with specific energy
High and low temperature performance is good, pollution-free, security performance is superior and storage and long working life, the advantages that energy utilization rate is high.Lithium from
The above-mentioned advantage of sub- secondary cell, promotes scientists from all over the world competitively to study, to promote the quick hair of lithium ion secondary battery
Exhibition.Since the advent of the world, in the more than ten short years, lithium ion secondary battery has just been widely used in mobile phone, notebook
In the electronic products such as computer, electronic interpreter, automobile telephone；It navigates in some other key areas such as electric vehicle, aviation
It, the application in the fields such as military affairs also just under development.
The anode of lithium ion secondary battery is made frequently with stratiform cobalt acid lithium, lithium nickelate, lithium nickel cobalt dioxide or spinel lithium manganate
For active material.Due to the poorly conductive of these active materials itself, the internal resistance of electrode is larger, and depth of discharge is inadequate, active material
The utilization rate of material is low, and the residual capacity of electrode is big.Therefore, improve between active material and collector and active material particle it
Between electric conductivity it is most important, in research and development and actual production usually using in active material addition conductive agent realize.
The type and dosage of conductive agent have large effect to active material utilization and electrode specific capacity and multiplying power discharging behavior.Such as
The content of the conductive agent that fruit is added in the electrodes is too small, then electrode internal resistance cannot be effectively reduced, so that the utilization of active material
Rate is relatively low, and the specific capacity of electrode is not high.On the contrary, if the too high levels of the conductive agent being added in the electrodes, active material
Utilization rate will be higher, but since content is few in the electrodes for activating agent, the specific capacity of battery be will also decrease.
The characteristics such as graphite, acetylene black and carbon fiber conductive good, density is small, stable structure and chemical stability,
It is often used as the conductive agent of lithium ion secondary battery anode material.In order to make full use of active material, the internal resistance of electrode is reduced, this
The a little weight percentages of conductive agent in the electrodes generally reach 5% or even 30%, and the use of a large amount of conductive agents certainly will cause to glue
The increase for tying agent dosage, causes the energy density of lithium ion secondary battery lower.
Summary of the invention
The purpose of the present invention is to provide a kind of dosage of reduction conductive agent in lithium ion secondary battery anode material, mention
The preparation method of the lithium ion battery of the energy density of high-lithium ion secondary cell.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method of lithium ion battery, comprising the following steps:
1) by positive active material, carbon nanotubes electrocondution slurry, binder according to 95%-99%:0.5%-2.5%:
The mass ratio of 0.5%-2.5% is mixed with solvent, is configured to anode sizing agent；The anode sizing agent is coated in plus plate current-collecting body
On, it is dried, roll-in, cutting obtain anode pole piece；
2) by negative electrode active material, carbon nanotubes electrocondution slurry, binder according to 90%-97%:0.5%-2%:
The mass ratio of 0.5%-2% is mixed with solvent, is configured to negative electrode slurry；The negative electrode slurry is coated on negative current collector,
It is dried, roll-in, cutting obtain cathode pole piece；
3) lithium ion battery is assembled using the anode pole piece, the cathode pole piece, diaphragm and electrolyte.
Further, the carbon nanotube pipe outside diameter of the carbon nanotubes electrocondution slurry is distributed 5-60nm, and distribution of lengths is
3-20 μm, the content of nanotube in the slurry is 4.5%-8%.
Further, the solvent is water, and the binder is carboxymethyl cellulose and butadiene-styrene rubber；Or the solvent is
N-Methyl pyrrolidone, the binder are to gather inclined fluorine vinyl chloride.
Further, the plus plate current-collecting body is aluminium foil, and the negative current collector is copper foil.
Further, the positive active material be cobalt acid lithium, LiMn2O4, LiFePO4, manganese nitrate lithium, ferric metasilicate lithium,
The one of which of ternary material, lithium sulfur materials.
Further, the configuration method of the anode sizing agent is as follows: the binder being added in the solvent, stirring is extremely
Uniformly；Then carbon nanotubes electrocondution slurry is added, is stirred until homogeneous；It is eventually adding positive active material, is beaten.
Further, the negative electrode active material is lithium titanate, graphite, soft carbon, hard carbon, mesocarbon material, silicon-carbon material
The one of which of material.
Further, the configuration method of the negative electrode slurry is as follows: the binder being added in the solvent, stirring is extremely
Uniformly；Then carbon nanotubes electrocondution slurry is added, is stirred until homogeneous；It is eventually adding negative electrode active material, is beaten.
Beneficial effects of the present invention:
The present invention, which is used, enhances battery pole piece containing CNT (carbon nanotube) electrocondution slurry, and carbon nanotube is by graphene film edge
Tube-like materials of the one kind with " concentric cylinder configuration " that seamless cylinder made of axis curling is nested layer by layer and is formed, diameter exist
Nanometer scale, length is in micron dimension, since carbon nanotube crystallinity is high, adds the big pi bond of delocalization existing for tube wall, thus carbon
Nanotube has good conductive property, in addition, since carbon nanotube has nanometer caliber and fibrous structure, carbon nanotube
For pipe outside diameter between 0.4-100nm, caliber is smaller, and carbon nanotube individual amount is more under Unit Weight, so adding on a small quantity
Carbon nanotube can form effective conductive network in the electrodes, be based on above-mentioned several points, and carbon nanotube is very suitable to make conductive agent；
Carbon nanotube conducting agent has apparent advantage compared with other conductive agents, with granular conductive agent such as acetylene black or graphite-phase
Than since carbon nanotube is threadiness, being easy to construct good conductive network in the electrodes, moreover, if building phase
With the conductive network of length, contact point between granular conductive agent such as acetylene black or graphite far more than fibrous conductive agent,
Cause resistance larger, generally, forms same conductive network, the dosage of fibrous conductive agent only needs granular conductive agent dosage
One third, compared with carbon fiber, although being all fibrous structure, the diameter of carbon fiber between 100-200nm,
The number of individuals of carbon fiber will form effective conductive network, carbon fiber than the number of individuals much less of carbon nanotube under Unit Weight
Additive amount more much bigger than the additive amount of carbon nanotube can be only achieved same effect.Furthermore carbon nanotube and carbon fiber
Electrical property is also different due to the difference of their structures.Carbon nanotube is as graphene film seamless cylinder layer made of axis curling
One kind that layer is nested and is formed has the tube-like materials of " concentric cylinder configuration ", and the carbon in carbon nanotube is sp2Hydridization, tube wall
Cylindrical surface forms the big pi bond of closure, and pi-electron is not on one carbon atom of localization Mr. Yu, under the action of external electric field, pi-electron from
One end of pipe moves to the other end and can be realized by the hyperconjugation of pi-electron, without crossing the energy barrier between graphite flake layer,
Thus transition process hinders less；And carbon fiber is that the seamless circular conical surface that is rolled by graphene film is stacked and formed, pi-electron from
One end of fiber moves to during the other end, it is necessary to cross the energy barrier between graphite flake layer, hinder it is larger, so, from microcosmic
The electric conductivity of analysis for carbon nanotubes is better than carbon fiber；Finally, because the outer diameter of carbon nanotube is smaller, specific surface and surface energy
Both greater than carbon fiber, when making conductive agent with carbon nanotube, carbon nanotube is easy to form conductive network so that conductive agent with just
Pole active contacts are close, to provide extremely convenient channel for the transport of electronics in the electrodes；
The preparation method of lithium ion battery provided by the invention is set about from battery pole piece electric conductivity is improved, and addition contains CNT
Conductive agent into pole piece, improve the active material ratio of battery pole piece itself.This method is generally applicable to various battery materials
System, and make simple, it is easy to accomplish large-scale industrial production.
Detailed description of the invention
In order to facilitate the understanding of those skilled in the art, the present invention will be further described below with reference to the drawings.
Fig. 1 is the flow diagram of the preparation method of lithium ion battery of the present invention.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with embodiment, it is clear that described reality
Applying example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is general
Logical technical staff all other embodiment obtained without creative efforts belongs to what the present invention protected
Range.
Referring to FIG. 1, the present invention provides a kind of preparation method of lithium ion battery, comprising the following steps:
1) by positive active material, containing CNT (carbon nanotube) electrocondution slurry, binder is according to (95%-99%):
(0.5%-2.5%): the mass ratio of (0.5%-2.5%) is mixed with solvent, is configured to anode sizing agent；The anode sizing agent is applied
It overlays on plus plate current-collecting body, is dried, roll-in, cutting obtain anode pole piece；
2) by negative electrode active material, containing CNT (carbon nanotube) electrocondution slurry, binder is according to (90%-97%):
(0.5%-2%): the mass ratio of (0.5%-2%) is mixed with solvent, is configured to negative electrode slurry；The negative electrode slurry is coated in
It on negative current collector, is dried, roll-in, cutting obtain cathode pole piece；
3) lithium ion battery is assembled using the anode pole piece, the cathode pole piece, diaphragm and electrolyte；
Specifically, the configuration method of the anode sizing agent is as follows: the binder being added in the solvent, is stirred to equal
It is even；Then it is added and contains CNT (carbon nanotube) electrocondution slurry, be stirred until homogeneous；It is eventually adding positive active material, is beaten；
The configuration method of the negative electrode slurry is as follows: the binder being added in the solvent, is stirred until homogeneous；Then
It is added and contains CNT (carbon nanotube) electrocondution slurry, be stirred until homogeneous；It is eventually adding negative electrode active material, is beaten；
Further, the positive active material be cobalt acid lithium, LiMn2O4, LiFePO4, manganese nitrate lithium, ferric metasilicate lithium,
The one of which of ternary material, lithium sulfur materials；The negative electrode active material is lithium titanate, graphite, soft carbon, hard carbon, mesocarbon
The one of which of material, silicon carbon material；The carbon nanotube pipe outside diameter containing CNT (carbon nanotube) electrocondution slurry is distributed 5-
60nm, distribution of lengths are 3-20 μm, and the content of nanotube in the slurry is 4.5%-8%；The solvent is water, the binder
For CMC (carboxymethyl cellulose) and SBR (butadiene-styrene rubber)；Or the solvent is N-Methyl pyrrolidone, the binder is
PVDF (gathers inclined fluorine vinyl chloride).The plus plate current-collecting body is aluminium foil, and the negative current collector is copper foil；
The electrolysis of the enhancing containing CNT (carbon nanotube) electrocondution slurry battery pole piece (including anode pole piece and cathode pole piece)
Liquid wettability principle is as follows: carbon nanotube is nested layer by layer as graphene film seamless cylinder made of axis curling and is formed
One kind have " concentric cylinder configuration " tube-like materials, diameter is in nanometer scale, and length is in micron dimension.Due to carbon nanotube
Crystallinity is high, and along with the big pi bond of delocalization existing for tube wall, thus carbon nanotube has good conductive property.In addition, due to carbon
Nanotube has nanometer caliber and fibrous structure, and for the pipe outside diameter of carbon nanotube between 0.4-100nm, caliber is smaller, unit
Carbon nanotube individual amount is more under weight, so effective conductive mesh can be formed in the electrodes by adding a small amount of carbon nanotube
Network.Based on above-mentioned several points, carbon nanotube is very suitable to make conductive agent.Carbon nanotube conducting agent has compared with other conductive agents
Apparent advantage.It is easy to granular conductive agent such as acetylene black or graphite-phase ratio since carbon nanotube is threadiness
Good conductive network is constructed in electrode.Moreover, if the conductive network of building equal length, granular conductive agent such as acetylene black
Or the contact point between graphite causes resistance larger far more than fibrous conductive agent.Generally, same conductive mesh is formed
Network, the dosage of fibrous conductive agent only need the one third of granular conductive agent dosage.Compared with carbon fiber, although being all
Fibrous structure, but the diameter of carbon fiber, between 100-200nm, the number of individuals of carbon fiber is than carbon nanotube under Unit Weight
Number of individuals much less.Form effective conductive network, the additive amount of carbon fiber ability more much bigger than the additive amount of carbon nanotube
Same effect can be reached.Furthermore carbon nanotube is also different because of the difference of their structures from the electrical property of carbon fiber.Carbon nanometer
Pipe is that one kind that is nested and being formed has " concentric cylinder configuration " layer by layer as graphene film seamless cylinder made of axis curling
Tube-like materials, the carbon in carbon nanotube is sp2Hydridization, the cylindrical surface of tube wall form the big pi bond of closure, pi-electron not localization
In on some carbon atom.Under the action of external electric field, pi-electron moves to the other end from one end of pipe can be by the super of pi-electron
Conjugation realizes, without crossing energy barrier between graphite flake layer, thus transition process hinder it is less；And carbon fiber is by stone
The seamless circular conical surface that black alkene piece is rolled into is stacked and is formed, and pi-electron is during moving to the other end from one end of fiber, it is necessary to more
The energy barrier between graphite flake layer is crossed, obstruction is larger, so, it is better than carbon fiber from the electric conductivity of micro-analysis carbon nanotube；
Finally, because the outer diameter of carbon nanotube is smaller, specific surface and surface can be both greater than carbon fiber, make conductive agent with carbon nanotube
When, carbon nanotube is easy to form conductive network, so that conductive agent contacts closely with positive active material, to be electronics in electricity
Transport in extremely provides extremely convenient channel, and when making conductive agent with carbon fiber, then it cannot reach and be led with carbon nanotube
Similar effect when electric agent.
In a specific embodiment, by manganate cathode material for lithium, electrocondution slurry containing CNT, PVDF according to 97.8:1.2:
1.0 mass ratio is mixed with N-Methyl pyrrolidone, is configured to anode sizing agent, specifically, PVDF is dissolved completely in N- first
In methyl pyrrolidone, then it is added and contains CNT to point slurry and be stirred until homogeneous, be eventually adding manganate cathode material for lithium and stir
Uniformly, after the completion of mashing, anode sizing agent is coated uniformly on aluminium foil, then positive pole is made in high temperature drying, roll-in, cutting
Piece；
Graphite, electrocondution slurry containing CNT, CMC, SBR are mixed according to the mass ratio of 96.5:0.5:1.5:1.5 with distilled water,
It is configured to negative electrode slurry, specifically, CMC is dissolved completely in distilled water first, electrocondution slurry containing CNT is then added and stirs
It mixes to uniform, is eventually adding graphite and is stirred until homogeneous, add SBR and be slowly stirred to uniform, after the completion of mashing, cathode is starched
Material is coated uniformly on copper foil, and then cathode pole piece is made in high temperature drying, roll-in, cutting；
In view of in present embodiment, the mass percent of the electrocondution slurry containing CNT is 4.5%, by obtained anode pole piece, is born
Pole pole piece is respectively labeled as positive 1 and minus 1；
In other embodiments, change CNT electrocondution slurry content, when the mass percent of CNT be 6.5% when,
According to the operating procedure in above-described embodiment, anode pole piece obtained, cathode pole piece are respectively labeled as positive 2 and minus 2；When CNT's
When mass percent is 8%, according to the operating procedure in above-described embodiment, anode pole piece obtained, cathode pole piece mark respectively
It is positive 3 and minus 3；
As reference object, when CNT is when the content of electrocondution slurry is 0%, according to the operating procedure in above-described embodiment,
Anode pole piece obtained, cathode pole piece are respectively labeled as positive 0 and minus 0；
It is assembled using the identical anode pole piece of electrocondution slurry containing CNT with cathode pole piece, is assembled into 18650 type cylinder electricity
Pond carries out film-making, winding, assembly, jet-bedding, point bottom, high-temperature baking, fluid injection, sealing stand and etc. after, carry out every electrical property
Test, test result is as follows table:
As a result as shown above, show after adding electrocondution slurry containing CNT, every electrical property of battery greatly promotes, specifically
, first charge discharge efficiency is promoted to 87.12-89.32%, and internal resistance is reduced to 11.7-13.7m Ω, and 3C charging constant current ratio is promoted to
90.12%-94.12%, 300 weeks cycle performances are promoted to 87.33%-92.33%, and with the increase of additive amount, every
Electrical property is also promoted steadily.
The preparation method of lithium ion battery provided by the invention is set about from battery pole piece electric conductivity is improved, and addition contains CNT
Conductive agent into pole piece, improve the active material ratio of battery pole piece itself.This method is generally applicable to various battery materials
System, and make simple, it is easy to accomplish large-scale industrial production.
Present invention disclosed above preferred embodiment is only intended to help to illustrate the present invention.There is no detailed for preferred embodiment
All details are described, are not limited the invention to the specific embodiments described.Obviously, according to the content of this specification,
It can make many modifications and variations.These embodiments are chosen and specifically described to this specification, is in order to better explain the present invention
Principle and practical application, so that skilled artisan be enable to better understand and utilize the present invention.The present invention is only
It is limited by claims and its full scope and equivalent.
Claims (8)
1. a kind of preparation method of lithium ion battery, which comprises the following steps:
1) by positive active material, carbon nanotubes electrocondution slurry, binder according to 95%-99%:0.5%-2.5%:
The mass ratio of 0.5%-2.5% is mixed with solvent, is configured to anode sizing agent；The anode sizing agent is coated in plus plate current-collecting body
On, it is dried, roll-in, cutting obtain anode pole piece；
2) by negative electrode active material, carbon nanotubes electrocondution slurry, binder according to 90%-97%:0.5%-2%:0.5%-
2% mass ratio is mixed with solvent, is configured to negative electrode slurry；The negative electrode slurry is coated on negative current collector, is dried
Dry, roll-in, cutting obtain cathode pole piece；
3) lithium ion battery is assembled using the anode pole piece, the cathode pole piece, diaphragm and electrolyte.
2. a kind of preparation method of lithium ion battery according to claim 1, which is characterized in that the carbon nanotubes is led
The carbon nanotube pipe outside diameter of plasma-based material is distributed 5-60nm, and distribution of lengths is 3-20 μm, and the content of nanotube in the slurry is
4.5%-8%.
3. a kind of preparation method of lithium ion battery according to claim 1, which is characterized in that the solvent is water, institute
Stating binder is carboxymethyl cellulose and butadiene-styrene rubber；Or the solvent is N-Methyl pyrrolidone, the binder is poly- inclined
Fluorine vinyl chloride.
4. a kind of preparation method of lithium ion battery according to claim 1, which is characterized in that the plus plate current-collecting body is
Aluminium foil, the negative current collector are copper foil.
5. a kind of preparation method of lithium ion battery according to claim 1, which is characterized in that the positive active material
For cobalt acid lithium, the one of which of LiMn2O4, LiFePO4, manganese nitrate lithium, ferric metasilicate lithium, ternary material, lithium sulfur materials.
6. a kind of preparation method of lithium ion battery according to claim 1, which is characterized in that the anode sizing agent is matched
It is as follows to set method: the binder being added in the solvent, is stirred until homogeneous；Then carbon nanotubes electrocondution slurry is added,
It is stirred until homogeneous；It is eventually adding positive active material, is beaten.
7. a kind of preparation method of lithium ion battery according to claim 1, which is characterized in that the negative electrode active material
For lithium titanate, graphite, soft carbon, hard carbon, mesocarbon material, silicon carbon material one of which.
8. a kind of preparation method of lithium ion battery according to claim 1, which is characterized in that the negative electrode slurry is matched
It is as follows to set method: the binder being added in the solvent, is stirred until homogeneous；Then carbon nanotubes electrocondution slurry is added,
It is stirred until homogeneous；It is eventually adding negative electrode active material, is beaten.
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| CN114361436A (en) * | 2021-12-31 | 2022-04-15 | 湖北钛时代新能源有限公司 | Square cylindrical lithium cobalt oxide battery and preparation method thereof |
| CN114361419A (en) * | 2021-12-31 | 2022-04-15 | 湖北钛时代新能源有限公司 | Square cylindrical silicon-carbon battery and preparation method thereof |
| CN115377401A (en) * | 2022-10-26 | 2022-11-22 | 楚能新能源股份有限公司 | Modified anode material and preparation method of lithium ion battery thereof |
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