CN105470476B - A kind of negative electrode of lithium ion battery for reducing irreversible capacity loss and preparation method thereof - Google Patents
A kind of negative electrode of lithium ion battery for reducing irreversible capacity loss and preparation method thereof Download PDFInfo
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- CN105470476B CN105470476B CN201510730367.3A CN201510730367A CN105470476B CN 105470476 B CN105470476 B CN 105470476B CN 201510730367 A CN201510730367 A CN 201510730367A CN 105470476 B CN105470476 B CN 105470476B
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of negative electrode of lithium ion battery for reducing irreversible capacity loss, the negative electrode slurry including negative current collector and coated on negative current collector surface, the negative electrode slurry is made of the component of following mass percentage：The sum of 25 ~ 45% negative electrode active materials, 0.3 ~ 5% conductive agent, 0.3 ~ 5% binding agent, 0 ~ 2% surfactant, 0.0001 ~ 0.01% lithium salts, 50 ~ 70% water, above-mentioned each component percentage composition are 100%.The negative electrode of lithium ion battery of the present invention can effectively reduce the irreversible capacity loss of battery, promote the energy density of battery.The present invention also provides a kind of negative electrode of lithium ion battery preparation methods for reducing irreversible capacity loss, and processing step is simple, and operability is strong, it is easy to accomplish, the industrialized production of lithium ion battery can be applied to scale completely.
Description
Technical field
The present invention relates to lithium ion battery preparing technical field, more particularly, to a kind of lithium for reducing irreversible capacity loss
Ion battery cathode and preparation method thereof.
Background technology
Directly positive/negative plate by diaphragm is assembled together in the manufacturing process of lithium ion battery at present, is lived in fluid injection
After change, irreversible capacity loss is inevitably generated.
One kind that the irreversible capacity loss of lithium ion battery is seen as lithium ion battery by existing technical solution is intrinsic
By forming SEI films, the portion capacity of battery has been lost in attribute so that first charge-discharge irreversible capacity increases, this serious shadow
Sound has arrived giving full play to for the energy content of battery.At present, numerous studies show that the SEI films that negative terminal surface is formed are irreversible capacity damages
The main cause of mistake.Different types of negative material irreversible loss percentage is slightly different, in general with high specific surface area
Negative material, irreversible capacity loss is larger.Although it can be coated at present by surface, improve cathode particle table itself
Face pattern and shape, optimization electrolyte solvent form and reduce irreversible capacity loss using means such as film for additive, but
It is that irreversible capacity loss percentage is still higher, such as Delanium 10 ~ 15%, soft carbon 10 ~ 20% etc..
For example, application publication number：CN103682347A, the Chinese patent of data of publication of application 2014.03.26 disclose one kind
Composite lithium ion battery cathode material, the composite lithium ion battery cathode material are mainly composed of the following components：Needle-shaped coke powder, weight
Amount percentage is 30%-50%；Natural spherical plumbago powder, weight percent 20%-30%；Isotropism coke powder, weight percent
Than for 15%-25%；Pitch coke powder, weight percent 10%-20%.The cathode is disadvantageous in that：In first charge-discharge
When can increase irreversible capacity, influence giving full play to for the energy content of battery.
Invention content
The present invention is to increase irreversible appearance in first charge-discharge to solve the negative electrode of lithium ion battery of the prior art
Amount, influences the problem of giving full play to of the energy content of battery, provides a kind of formulation optimization, can effectively reduce the irreversible capacity of battery
Loss promotes the negative electrode of lithium ion battery of the reduction irreversible capacity loss of the energy density of battery.
The present invention also provides a kind of negative electrode of lithium ion battery preparation method for reducing irreversible capacity loss, processing steps
Simply, operability is strong, it is easy to accomplish, the industrialized production of lithium ion battery can be applied to scale completely.
To achieve these goals, the present invention uses following technical scheme：
A kind of negative electrode of lithium ion battery for reducing irreversible capacity loss, including negative current collector and coated on negative pole currect collecting
The negative electrode slurry in body surface face, the negative electrode slurry are made of the component of following mass percentage：25 ~ 45% negative electrode active materials,
0.3 ~ 5% conductive agent, 0.3 ~ 5% binding agent, 0 ~ 2% surfactant, 0.0001 ~ 0.01% lithium salts, 50 ~ 70% water, above-mentioned each component
The sum of percentage composition is 100%.The negative electrode slurry formula of cathode is optimized in the present invention, particularly adds in negative electrode slurry
Lithium salts is added, these lithium salts can be formed uniformly one or more layers after negative electrode slurry is coated baking in cathode particle surface
Metastable state SEI membrane structures, after battery charging and discharging activates, metastable state SEI films through reform become more stable, be avoided that lithium
Part lithium ion is lost to form SEI films in ion battery in subsequent charge and discharge activation process, and electricity is effectively reduced so as to reach
The irreversible capacity loss in pond promotes the purpose of the energy density of battery.
Preferably, the negative electrode active material is one in Delanium, native graphite, composite graphite, soft carbon, hard carbon
Kind is a variety of.
Preferably, the conductive agent is SP, KS-6, ECP, carbon nanotube, one kind in gas-phase growth of carbon fibre or more
Kind.
Preferably, the binding agent is SBR butadiene-styrene rubber or LA133 aqueous binders.
Preferably, the surfactant is sodium carboxymethylcellulose or polyvinylpyrrolidone.
Preferably, the lithium salts is LiOH, Li2CO3、LiF、Li2C2O4、（CH2OCO2Li）2、HCOLi、
LiCH2CH2OCO2Li、CH3OCO2It is one or more in Li.
A kind of negative electrode of lithium ion battery preparation method for reducing irreversible capacity loss, the specific steps are：
（1）Lithium salts is dissolved in the water for accounting for total Water 10 ~ 20%, obtains lithium salt solution, for use.
（2）Surfactant and remaining water are added in conductive agent after mixing to be uniformly dispersed to form conducting resinl.
（3）After negative electrode active material dispersion is added in conducting resinl, binding agent and lithium salt solution are added in, it is true after stirring evenly
Empty deaeration, obtains negative electrode slurry.
（4）Negative electrode slurry is evenly applied to negative current collector surface, is dried to get negative electrode of lithium ion battery.
Therefore, the present invention has the advantages that：
（1）The negative electrode slurry formula of cathode is optimized in the present invention, and lithium salts is particularly added in negative electrode slurry,
These lithium salts can be formed uniformly one or more layers metastable state in cathode particle surface after negative electrode slurry is coated baking
SEI membrane structures, after battery charging and discharging activates, metastable state SEI films become more stable through reforming, and are avoided that lithium ion battery
In subsequent charge and discharge activation process be lost part lithium ion to form SEI films, so as to reach effectively reduce battery can not
Inverse capacitance loss promotes the purpose of the energy density of battery；
（2）The preparation method of the present invention, processing step is simple, and operability is strong, it is easy to accomplish, it can be transported completely with scale
For the industrialized production of lithium ion battery.
Specific embodiment
Below by specific embodiment, the present invention will be further described.
In the present invention, if not refering in particular to, all percentages are unit of weight, and all devices and raw material can be purchased from market
It obtains or the industry is common, the method in following embodiments is this field conventional method unless otherwise instructed.
Embodiment 1
A kind of negative electrode of lithium ion battery for reducing irreversible capacity loss, including negative current collector and coated on negative pole currect collecting
The negative electrode slurry in body surface face, negative electrode slurry are made of the component of following mass percentage：25% negative electrode active material, 1% is conductive
Agent, 2% binding agent, 1.9999% surfactant, 0.0001% lithium salts, 70% water, wherein, negative electrode active material is Delanium；
Conductive agent is SP；Binding agent is LA133 aqueous binders；Surfactant is sodium carboxymethylcellulose；Lithium salts for LiOH and
Li2CO3（Mass ratio 1:1）；
The negative electrode of lithium ion battery of the reduction irreversible capacity loss is made by the following method：
（1）Lithium salts is dissolved in the water for accounting for total Water 10%, obtains lithium salt solution, for use；
（2）Surfactant and remaining water are added in conductive agent after mixing to be uniformly dispersed to form conducting resinl；
（3）After negative electrode active material dispersion is added in conducting resinl, binding agent and lithium salt solution are added in, it is true after stirring evenly
Empty deaeration, obtains negative electrode slurry；
（4）Negative electrode slurry is evenly applied to negative current collector surface, is dried to get negative electrode of lithium ion battery.
Embodiment 2
A kind of negative electrode of lithium ion battery for reducing irreversible capacity loss, including negative current collector and coated on negative pole currect collecting
The negative electrode slurry in body surface face, negative electrode slurry are made of the component of following mass percentage：45% negative electrode active material, 0.3% leads
Electric agent, 2.69% binding agent, 2% surfactant, 0.01% lithium salts, 50% water, wherein, negative electrode active material is Delanium and day
Right graphite（Mass ratio 1：1）；Conductive agent is KS-6 and gas-phase growth of carbon fibre（Mass ratio 3:1）；Binding agent is SBR butylbenzene rubbers
Glue；Surfactant is sodium carboxymethylcellulose；Lithium salts is LiOH, Li2CO3With（CH2OCO2Li）2（Mass ratio 1:1:1）；
The negative electrode of lithium ion battery of the reduction irreversible capacity loss is made by the following method：
（1）Lithium salts is dissolved in the water for accounting for total Water 15%, obtains lithium salt solution, for use；
（2）Surfactant and remaining water are added in conductive agent after mixing to be uniformly dispersed to form conducting resinl；
（3）After negative electrode active material dispersion is added in conducting resinl, binding agent and lithium salt solution are added in, it is true after stirring evenly
Empty deaeration, obtains negative electrode slurry；
（4）Negative electrode slurry is evenly applied to negative current collector surface, is dried to get negative electrode of lithium ion battery.
Embodiment 3
A kind of negative electrode of lithium ion battery for reducing irreversible capacity loss, including negative current collector and coated on negative pole currect collecting
The negative electrode slurry in body surface face, negative electrode slurry are made of the component of following mass percentage：29.995% negative electrode active material, 0.3
~ 5% conductive agent, 0.3 ~ 5% binding agent, 0.005% lithium salts, 60% water, wherein, negative electrode active material is Delanium and soft carbon（Matter
Measure ratio 1:3）；Conductive agent is SP, KS-6 and ECP（Mass ratio 1：3：1）；Binding agent is LA133 aqueous binders；Lithium salts is
HCOLi and LiCH2CH2OCO2Li（Mass ratio 2：3）；
The negative electrode of lithium ion battery of the reduction irreversible capacity loss is made by the following method：
（1）Lithium salts is dissolved in the water for accounting for total Water 20%, obtains lithium salt solution, for use；
（2）Surfactant and remaining water are added in conductive agent after mixing to be uniformly dispersed to form conducting resinl；
（3）After negative electrode active material dispersion is added in conducting resinl, binding agent and lithium salt solution are added in, it is true after stirring evenly
Empty deaeration, obtains negative electrode slurry；
（4）Negative electrode slurry is evenly applied to negative current collector surface, is dried to get negative electrode of lithium ion battery.
Embodiment 4
A kind of negative electrode of lithium ion battery for reducing irreversible capacity loss, including negative current collector and coated on negative pole currect collecting
The negative electrode slurry in body surface face, negative electrode slurry are made of the component of following mass percentage：35% negative electrode active material, 0.3% leads
Electric agent, 0.3% binding agent, 1% surfactant, 0.01% lithium salts, 63.39% water, wherein, negative electrode active material is soft carbon and hard carbon
（Mass ratio 2:3）；Conductive agent is SP, ECP and carbon nanotube（Mass ratio 1：1：1）；Binding agent is SBR butadiene-styrene rubber；It lives on surface
Property agent be polyvinylpyrrolidone；Lithium salts is LiF, Li2C2O4、CH3OCO2Li（Mass ratio 1:1:3）；
The negative electrode of lithium ion battery of the reduction irreversible capacity loss is made by the following method：
（1）Lithium salts is dissolved in the water for accounting for total Water 10%, obtains lithium salt solution, for use；
（2）Surfactant and remaining water are added in conductive agent after mixing to be uniformly dispersed to form conducting resinl；
（3）After negative electrode active material dispersion is added in conducting resinl, binding agent and lithium salt solution are added in, it is true after stirring evenly
Empty deaeration, obtains negative electrode slurry；
（4）Negative electrode slurry is evenly applied to negative current collector surface, is dried to get negative electrode of lithium ion battery.
The negative electrode of lithium ion battery of the present invention is applied in conventional phosphoric acid lithium iron battery, irreversible capacity loss percentage
3 ~ 5% can be reduced to, compared to Delanium（Irreversible capacity loss percentage 10 ~ 15%）, soft carbon（Irreversible capacity loss hundred
Divide ratio 10 ~ 20%）Conventional anodes are waited, effect is very notable.
Embodiment described above is a kind of preferable scheme of the present invention, and not the present invention is made in any form
Limitation also has other variants and remodeling under the premise of without departing from the technical solution recorded in claim.
Claims (4)
1. a kind of negative electrode of lithium ion battery for reducing irreversible capacity loss, including negative current collector and coated on negative current collector
The negative electrode slurry on surface, which is characterized in that the negative electrode slurry is made of the component of following mass percentage：25 ~ 45% cathode
Active material, 0.3 ~ 5% conductive agent, 0.3 ~ 5% binding agent, 0 ~ 2% surfactant, 0.0001 ~ 0.01% lithium salts, 50 ~ 70% water,
The sum of above-mentioned each component percentage composition is 100%；
The lithium salts is LiOH, Li2CO3、LiF、Li2C2O4、（CH2OCO2Li）2、HCOLi、LiCH2CH2OCO2Li、CH3OCO2Li
In it is one or more；
The surfactant is sodium carboxymethylcellulose or polyvinylpyrrolidone；
The negative electrode of lithium ion battery preparation method of the reduction irreversible capacity loss, the specific steps are：
（1）Lithium salts is dissolved in the water for accounting for total Water 10 ~ 20%, obtains lithium salt solution, for use；
（2）Surfactant and remaining water are added in conductive agent after mixing to be uniformly dispersed to form conducting resinl；
（3）After negative electrode active material dispersion is added in conducting resinl, binding agent and lithium salt solution are added in, rear vacuum is stirred evenly and takes off
Bubble, obtains negative electrode slurry；
（4）Negative electrode slurry is evenly applied to negative current collector surface, is dried to get negative electrode of lithium ion battery.
A kind of 2. negative electrode of lithium ion battery for reducing irreversible capacity loss according to claim 1, which is characterized in that institute
It is one or more in Delanium, native graphite, composite graphite, soft carbon, hard carbon to state negative electrode active material.
A kind of 3. negative electrode of lithium ion battery for reducing irreversible capacity loss according to claim 1, which is characterized in that institute
It is one or more in SP, KS-6, ECP, carbon nanotube, gas-phase growth of carbon fibre to state conductive agent.
A kind of 4. negative electrode of lithium ion battery for reducing irreversible capacity loss according to claim 1, which is characterized in that institute
Binding agent is stated as SBR butadiene-styrene rubber or LA133 aqueous binders.
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| CN106684333B (en) * | 2017-01-13 | 2019-12-13 | 天津中聚新能源科技有限公司 | Lithium ion battery cathode slurry and preparation method thereof |
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| CN107910520A (en) * | 2017-11-10 | 2018-04-13 | 江苏华富储能新技术股份有限公司 | A kind of lithium ion battery cathode slurry, negative material and preparation method thereof |
| CN107732154A (en) * | 2017-11-10 | 2018-02-23 | 江苏华富储能新技术股份有限公司 | Small lithium ion battery of loss of capacitance and preparation method thereof after a kind of circulation electric discharge |
| CN108199004A (en) * | 2017-12-25 | 2018-06-22 | 深圳市山木新能源科技股份有限公司 | The manufacturing method and electrode slice of electrode slice |
| EP3933967A4 (en) * | 2019-02-28 | 2022-04-20 | Panasonic Corporation | Slurry for non-aqueous electrolyte secondary cell, method for manufacturing slurry for non-aqueous electrolyte secondary cell, electrode for non-aqueous electrolyte secondary cell, and non-aqueous electrolyte secondary cell |
| CN110190245B (en) * | 2019-06-17 | 2020-11-24 | 珠海格力电器股份有限公司 | Negative electrode slurry containing stable lithium salt, preparation method, negative electrode plate and lithium ion battery |
| CN110492103A (en) * | 2019-08-19 | 2019-11-22 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of lithium ion battery silicon-carbon cathode binder and products thereof and application |
| CN112768642A (en) * | 2019-11-01 | 2021-05-07 | 广州汽车集团股份有限公司 | Negative electrode material and preparation method thereof, negative electrode plate, lithium ion battery cell and lithium ion battery pack and application thereof |
| CN114094110B (en) * | 2022-01-24 | 2022-04-22 | 河南电池研究院有限公司 | Graphite cathode for solid lithium ion battery |
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