CN105870454A - Application method of graphene as conductive agent to positive electrode slurry of lithium ion battery - Google Patents
Application method of graphene as conductive agent to positive electrode slurry of lithium ion battery Download PDFInfo
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- CN105870454A CN105870454A CN201610387089.0A CN201610387089A CN105870454A CN 105870454 A CN105870454 A CN 105870454A CN 201610387089 A CN201610387089 A CN 201610387089A CN 105870454 A CN105870454 A CN 105870454A
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- conductive agent
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- lithium ion
- ion battery
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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 an application method of graphene as a conductive agent to positive electrode slurry of a lithium ion battery. The slurry is prepared from 90-97% of active substances, 1-4% of a conductive agent, and 1-5% of a binding agent by mass through the steps of dispersing the binding agent, dispersing the conductive agent, and dispersing the active substances. The prepared slurry has good uniformity, and excellent stability. According to the lithium battery produced by the positive electrode slurry, the internal resistance of the battery can be reduced obviously, and the high current discharging performance, the low temperature performance and the high current charging and discharging cycling performance of the battery can be improved.
Description
Technical field
The invention belongs to lithium ion battery material manufacturing technology field, be specifically related to a kind of Graphene as conductive agent for the method for lithium ion battery anode glue size.
Background technology
Lithium ion battery have that specific capacity is big, discharge voltage is high and steady, cryogenic property is good, environmental friendliness, safety, life-span length, self discharge are little and ni-mh, the unrivaled advantage of NI-G secondary cell.Since within 1991, coming out, through the development in more than ten years, lithium ion battery has dominated the market of compact portable battery.
The positive electrode of lithium ion battery is generally transition-metal oxide, such as: LiCoO2, LiNiO2, LiMnO2 and LiNixCoyMn(1-x-y) O2 etc., and the phosphate of transition metal, such as: LiMPO4；They electrical conductivity are low, usually quasiconductor or insulator.The most extremely ion and the mixed conductor of electronics, electron conduction is relevant with positive conductive quality；Ionic conductivity is relevant with the pore volume of positive pole, and loose structure can provide the storage of electrolyte, provides buffer ions source for electrode fast reaction.Conductive agent is in the electric conductivity of the effect mainly raising positive pole of positive pole.
Excellent conductive agent needs possess following feature: one, electrical conductivity is higher, and the material of high conductivity can improve the migration rate of electronics；Two, particle diameter is less, and the material of small particle can fill the space of lithium ion battery positive and negative electrode material, makes the contact between material preferable, it is easy to the abjection of lithium ion, embedding；Three, high-specific surface area, the big material of specific surface area preferably and positive and negative electrode material can be equally easy to the holding of electrolyte, it is simple to the deintercalation of lithium ion and electron transfer；Four, it is easily dispersed, is prone to break up and disperse in positive and negative electrode material configuration slurry process, can be preferably together with positive and negative electrode material mixing；Five, high stability, during lithium ion battery discharge and recharge, energy stable existence, will not occur change in volume to affect the cycle performance of battery.
Graphene is the material that a kind of carbon atom arrangement as the graphite of the three dimensional structure carbon allotrope being naturally occurring in nature becomes the hexagon plane structure of two-dimensional sheet form.The carbon atom of Graphene forms SP2 key, and has the plane sheets form of monoatomic thickness.Graphene has significantly excellent electric conductivity and a heat conductivity, and physical property (such as excellent mechanical strength, flexibility, elasticity, depending on the quantization transparency of thickness, high-specific surface area etc.) can be explained the specific bonding structure of atom by being present in Graphene.In four peripheral electrons of the carbon constituting Graphene three form sp2 hybrid orbital thus have σ key, and a remaining electronics and surrounding carbon atom form a π key, to provide a hexagon two-dimensional structure.Therefore, Graphene has a band structure being different from other carbon allotrope, and does not have band gap (band gap) thus show the electric conductivity of excellence；But, Graphene is a kind of semi-metallic, and wherein the fermi level density of states of electronics is 0, and therefore, depends on whether it is doped, and can easily vary electrical characteristics.Correspondingly, owing to Graphene can be widely used in automobile, the energy, aviation, building, pharmacy and iron and steel domain, and various electric and electronic field, such as a new generation's material, capacitor, electromagnetic shielding material, sensor, display etc., it may replace silicon electric and electronic material, therefore applies the existing many research of technology of Graphene carrying out in various fields.
Summary of the invention
Based on above-mentioned present situation, the present invention proposes a kind of Graphene as conductive agent for the method for lithium ion battery anode glue size.The present invention using brand-new Graphene as conductive agent materials application in lithium ion battery anode glue size, it is provided that rational proportioning between active substance and other adjuvant.
Above-mentioned Graphene, is carried out for the method for lithium ion battery anode glue size as follows as conductive agent:
(1) first the solvent of aequum 70%～90% is put in agitator, add the desired amount of binding agent, stir 1～5 hour；
(2), after binding agent dispersion completely, add the desired amount of conductive agent Graphene, stir 0.5～2 hour；
(3), after conductive agent dispersion completely, add the desired amount of active substance, stir 2～6 hours.After all components dispersion completely, it is suitably added residual solvent and adjusts slurry viscosity to 4000～7000Mpa S.
In above-mentioned steps 1, solvent is N-Methyl pyrrolidone (NMP), and binding agent is Kynoar (PVDF).
In above-mentioned steps 2, active substance is LiCoO2、LiNiO2、LiMn2O4、LiNixCoyMn(1-x-y)O2And LiFePO4In one or more mixture.
In above-mentioned steps 1 and step 2, the mass ratio of each component of active substance, conductive agent, binding agent is followed successively by (90-97): (1-4): (1-5), and solvent is the 60%～90% of above-mentioned each component weight.
In above steps, mixing plant is double-planet de-airing mixer, and slurry temperature is that the method for the thermostatical circulating water that utilization is passed through relevant temperature to planet stirring bucket controls.
The invention has the beneficial effects as follows: the present invention for graphene conductive agent at the actually used offer of anode material for lithium-ion batteries rationally reliable formula and preparation method thereof, use graphene conductive agent can significantly reduce the internal resistance of battery, improve the heavy-current discharge performance of battery, cryogenic property, and high current charge-discharge cycle performance.
Accompanying drawing explanation
Accompanying drawing 1 is the loop test capability retention comparison diagram of embodiment 1 and comparative example 1.
Detailed description of the invention
Below the preferred embodiment of the present invention is elaborated.
Embodiment 1
Graphene is used for lithium ion battery anode glue size as conductive agent, according to LiFePO4: the mass ratio of Graphene: PVDF=95:2.5:3.5, solvent NMP is the 90% of above-mentioned each component total amount.Binding agent jitter time is 3 hours, and the graphene dispersion time is 2 hours, and active substance jitter time is 4 hours, and final slurry viscosity is 6594Mpa S.
Comparative example 1
According to conventional lithium iron phosphate cathode slurry production technology, according to LiFePO4: the mass ratio of SP:PVDF=95:2.5:3.5, solvent NMP is the 90% of above-mentioned each component total amount.Binding agent jitter time is 3 hours, and the graphene dispersion time is 2 hours, and active substance jitter time is 4 hours, and final slurry viscosity is 6127Mpa S.
18650 type cylindrical lithium batteries obtained by embodiment 1 and comparative example 1 are carried out electrical performance testing, its charge and discharge under 1C, the circulation volume conservation rate of 1000 times, embodiment 1 is 97.92%, comparative example 1 is 95.23%, comparing result is as shown in Fig. 1, and energy density and inner walkway comparing result are as shown in table 1.
Embodiment 2
Graphene is used for lithium ion battery anode glue size as conductive agent, according to LiCoO2: the mass ratio of Graphene: PVDF=95.7:2.3:2.0, solvent NMP is the 65% of above-mentioned each component total amount.Binding agent jitter time is 2 hours, and the graphene dispersion time is 1 hour, and active substance jitter time is 4 hours, and final slurry viscosity is 5972Mpa S.
Comparative example 2
According to conventional lithium cobaltate cathode slurry production process, according to LiCoO2: the mass ratio of SP:PVDF=95.7:2.3:2.0, solvent NMP is the 65% of above-mentioned each component total amount.Binding agent jitter time is 2 hours, and conductive agent jitter time is 1 hour, and active substance jitter time is 4 hours, and final slurry viscosity is 5326Mpa S.
18650 type cylindrical batteries obtained by embodiment 2 and comparative example 2 are carried out electrical performance testing, its charge and discharge under 1C, the circulation volume conservation rate of 1000 times, embodiment 1 is 97.23%, comparative example 1 is 93.23%, and energy density and inner walkway comparing result are as shown in table 1.
The energy density of each embodiment of table 1 and comparative example and inner walkway comparing result
As can be seen from the above table, the lithium battery obtained by anode sizing agent using the inventive method to prepare, energy density is above the lithium battery obtained by conventional cathode slurry production process, internal resistance is below the lithium battery obtained by conventional cathode slurry production process.
The graphene conductive agent slurry that the present invention provides has good conductivity, gram volume is high, equipment simple, low cost, the feature such as applied widely, cannot be only used on general digital lithium ion battery product, it is also possible to be applied in power and energy storage lithium ion battery.
It will be recognized by one skilled in the art that above example is intended merely to the present invention is described, and be not intended as limitation of the invention, as long as within the scope of the invention, change, deformation to above example all will fall in protection scope of the present invention.
Claims (5)
1. the method that Graphene is used for lithium ion battery anode glue size as conductive agent, its preparation process is as follows:
(1) first the solvent of aequum 70%～90% is put in agitator, add the desired amount of binding agent, stir 1～5 hour；
(2), after binding agent dispersion completely, add the desired amount of conductive agent Graphene, stir 0.5～2 hour；
(3) after conductive agent dispersion completely, add the desired amount of active substance, stir 2～6 hours, after all components dispersion completely, be suitably added residual solvent adjustment slurry viscosity to 4000～7000Mpa S.
2. the method being used for lithium ion battery anode glue size according to the Graphene described in claim 1 as conductive agent, is characterized in that: in step 1, solvent is N-Methyl pyrrolidone (NMP), binding agent is Kynoar (PVDF).
3. the method being used for lithium ion battery anode glue size according to the Graphene described in claim 1 as conductive agent, is characterized in that: in step 2, active substance is LiCoO2、LiNiO2、LiMn2O4、LiNixCoyMn(1-x-y )O2And LiFePO4In one or more mixture.
4. the method being used for lithium ion battery anode glue size according to the Graphene described in claim 1 as conductive agent, it is characterized in that: in step 1 and step 2, the mass ratio of each component of active substance, conductive agent, binding agent is followed successively by (90-97): (1-4): (1-5), and solvent is the 60%～90% of above-mentioned each component weight.
5. the method being used for lithium ion battery anode glue size according to the Graphene described in claim 1 as conductive agent, it is characterized in that: in step (1), (2), (3), mixing plant is double-planet de-airing mixer, and slurry temperature is that the method for the thermostatical circulating water that utilization is passed through relevant temperature to planet stirring bucket controls.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610387089.0A CN105870454A (en) | 2016-06-03 | 2016-06-03 | Application method of graphene as conductive agent to positive electrode slurry of lithium ion battery |
| PCT/CN2016/092376 WO2017206307A1 (en) | 2016-06-03 | 2016-07-29 | Method for applying graphene as conductive agent to anode slurry for lithium-ion batteries |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610387089.0A CN105870454A (en) | 2016-06-03 | 2016-06-03 | Application method of graphene as conductive agent to positive electrode slurry of lithium ion battery |
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| CN105870454A true CN105870454A (en) | 2016-08-17 |
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| CN201610387089.0A Withdrawn CN105870454A (en) | 2016-06-03 | 2016-06-03 | Application method of graphene as conductive agent to positive electrode slurry of lithium ion battery |
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| WO (1) | WO2017206307A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106450333A (en) * | 2016-10-28 | 2017-02-22 | 合肥国轩电池材料有限公司 | Lithium battery anode slurry and slurry mixing method thereof |
| CN107256966A (en) * | 2017-05-17 | 2017-10-17 | 常州第六元素材料科技股份有限公司 | A kind of anode slice of lithium ion battery and preparation method thereof, lithium ion battery anode glue size and its method |
| CN114420930A (en) * | 2021-12-23 | 2022-04-29 | 山东精工电子科技有限公司 | Dispersing method of conductive agent in lithium ion battery slurry and lithium ion battery slurry |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114577867B (en) * | 2022-02-15 | 2023-10-03 | 厦门大学 | Method for detecting Chang Liangji g capacity of fluorocarbon material |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101794874A (en) * | 2009-08-25 | 2010-08-04 | 天津大学 | Electrode with grapheme as conductive additive and application thereof in lithium ion battery |
| TWI539649B (en) * | 2014-11-13 | 2016-06-21 | Get Green Energy Corp Ltd | An electrode material suitable for a lithium battery, a method for manufacturing the same, and a method for manufacturing the same Electrode for lithium batteries |
| CN104466087B (en) * | 2014-12-04 | 2017-07-07 | 中航锂电（洛阳）有限公司 | A kind of lithium ion battery anode glue size and its preparation method and application |
| CN105185951A (en) * | 2015-08-24 | 2015-12-23 | 深圳市斯诺实业发展有限公司 | Preparation method of lithium battery cathode slurry |
| CN105161676A (en) * | 2015-08-25 | 2015-12-16 | 田东 | Preparation method for lithium iron phosphate cathode slurry |
-
2016
- 2016-06-03 CN CN201610387089.0A patent/CN105870454A/en not_active Withdrawn
- 2016-07-29 WO PCT/CN2016/092376 patent/WO2017206307A1/en active Application Filing
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106450333A (en) * | 2016-10-28 | 2017-02-22 | 合肥国轩电池材料有限公司 | Lithium battery anode slurry and slurry mixing method thereof |
| CN107256966A (en) * | 2017-05-17 | 2017-10-17 | 常州第六元素材料科技股份有限公司 | A kind of anode slice of lithium ion battery and preparation method thereof, lithium ion battery anode glue size and its method |
| CN107256966B (en) * | 2017-05-17 | 2021-03-23 | 常州第六元素材料科技股份有限公司 | Lithium ion battery positive pole piece and preparation method thereof |
| CN114420930A (en) * | 2021-12-23 | 2022-04-29 | 山东精工电子科技有限公司 | Dispersing method of conductive agent in lithium ion battery slurry and lithium ion battery slurry |
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| WO2017206307A1 (en) | 2017-12-07 |
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