CN106159214B - Electrode slurry presoma, electrode slurry and preparation method thereof, electrode and lithium ion battery - Google Patents
Electrode slurry presoma, electrode slurry and preparation method thereof, electrode and lithium ion battery Download PDFInfo
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- CN106159214B CN106159214B CN201510146335.9A CN201510146335A CN106159214B CN 106159214 B CN106159214 B CN 106159214B CN 201510146335 A CN201510146335 A CN 201510146335A CN 106159214 B CN106159214 B CN 106159214B
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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
- H01M4/364—Composites as mixtures
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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
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0473—Filling tube-or pockets type electrodes; Applying active mass in cup-shaped terminals
- H01M4/0478—Filling tube-or pockets type electrodes; Applying active mass in cup-shaped terminals with dispersions, suspensions or pastes
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0473—Filling tube-or pockets type electrodes; Applying active mass in cup-shaped terminals
- H01M4/048—Filling tube-or pockets type electrodes; Applying active mass in cup-shaped terminals with dry powder
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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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 present invention relates to field of batteries, a kind of electrode slurry presoma is specifically provided, the electrode slurry presoma includes packaging bag film and the electrode material that is sealed in the packaging bag film, and the packaging bag film dissolves in organic solvent.The present invention provides a kind of electrode slurrys and preparation method thereof, this method comprises: (1) is dissolved the polymer material containing Kynoar to obtain solution using organic solvent, the solution are formed a film to obtain packaging bag film；(2) electrode material is sealed with the packaging bag film, obtains electrode slurry presoma；(3) the electrode slurry presoma is added in organic solvent and is dissolved to obtain electrode slurry.The present invention provides a kind of electrode and lithium ion batteries.The electrode slurry uniformity of the invention is high, mechanical adhesion is good.
Description
Technical field
The present invention relates to a kind of electrode slurry presoma, a kind of electrode slurry and preparation method thereof, a kind of electrode and one kind
Lithium ion battery.
Background technique
Component is distributed uniform electrode slurry, directly affects the comprehensive performance of lithium ion battery.Current feeding mode is main
For following two: A) binder solution is prepared, conductive agent is added and mixes, positive active material mixing is added and is slurried；B) binder
It is mixed with conductive agent and positive active material, mechanical stirring premix, solvent mixing is added and is slurried.
There are following several big disadvantages: 1. option A for current feeding mode): slurry viscosity depends primarily on binder, the program
The slurry viscosity of preparation is horizontal whole higher, relies on removing bubbles from slurry device, and mixing time is longer；2. option b): material mixing workshop
Dust pollution is serious, is unfavorable for first-line staff's health, and mixing plant is easily lost, and energy consumption is high；3. two schemes are multiple throwing
Material, process is cumbersome, and error rate is high, may introduce moisture and impurity in mixing process；4. two schemes, for gel component, only
It can feed intake by hand, be unfavorable for quickly producing；5. two schemes, recovery processing various types of materials packaging easily causes secondary pollution, and increases
Addition sheet.
Summary of the invention
It is an object of the invention to overcome the deficiencies of existing technologies, provide that a kind of uniformity is more preferable, mechanical adhesion is stronger
Electrode slurry.
To realize foregoing purpose, in a first aspect, the present invention provides a kind of electrode slurry presoma, before the electrode slurry
The electrode material that body includes packaging bag film and is sealed in the packaging bag film is driven, the packaging bag film dissolves in organic molten
Agent.
Second aspect, the present invention provides a kind of electrode slurry, the electrode slurry is by by electrode slurry of the present invention
Material precursor dissolution obtains in organic solvent.
The third aspect, the present invention provides a kind of preparation methods of electrode slurry, this method comprises:
(1) it is dissolved the polymer material containing Kynoar to obtain solution using organic solvent, by the solution
It is formed a film to obtain packaging bag film；
(2) electrode material is sealed with the packaging bag film, obtains electrode slurry presoma；
(3) the electrode slurry presoma is added in organic solvent and is dissolved to obtain electrode slurry.
Fourth aspect, the present invention provides a kind of electrode, the electrode is coated in electricity by electrode slurry of the present invention
It on the collector of pole, then dried, roll-in, cut to obtain.
5th aspect, the present invention provides a kind of lithium ion battery, which contains electrode of the present invention.
The electrode slurry uniformity of the invention is high, mechanical adhesion is good.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
As previously mentioned, the electrode slurry presoma includes packaging bag the present invention provides a kind of electrode slurry presoma
Film and the electrode material being sealed in the packaging bag film, the packaging bag film dissolve in organic solvent.
In the present invention, the packaging bag film dissolves in organic solvent and refers to that packaging bag film can be dissolved by an organic solvent.
In the present invention, the electrode slurry presoma refers to the composition for being used to prepare electrode slurry.
Electrode slurry presoma according to the present invention, optional wider range of the type of the organic solvent, this field are normal
It advises the organic solvent used and is used equally for the present invention, for the present invention, the preferably described organic solvent is N-Methyl pyrrolidone, master
Chain is no more than one of ketone, dimethyl sulfoxide, dimethylformamide, dimethyl acetamide and the tetrahydrofuran of 6 carbon atoms
It is or a variety of, wherein the ketone that main chain is no more than 6 carbon atoms is, for example, acetone etc..N- is used in a specific embodiment of the present invention
Methyl pyrrolidone makees exemplary illustration.
Electrode slurry presoma according to the present invention, the electrode material in the preferably described packaging bag film are powdered or paste
Object.
Electrode slurry presoma according to the present invention, the preferably described packaging bag film with a thickness of 0.05-0.5mm, more preferably
For 0.1-0.3mm.
Electrode slurry presoma according to the present invention, the present invention is to the material of the packaging bag film without particular/special requirement, routine
The polymer material that film can be made be used equally for the present invention, for the present invention, the material of the preferably described packaging bag film includes
Kynoar (PVDF), with the weight of packaging bag film, the content of the Kynoar is 40-100 weight
Measure %, preferably 60-90 weight %.
Electrode slurry presoma according to the present invention, wherein the material of the preferred packaging bag film further includes organic addition
Agent, the preferably described organic additive be selected from Vingon (PVDC), polyvinyl alcohol (PVA), polyethylene glycol, polyacrylate,
One of polymethacrylates, polyurethane, Pioloform, polyvinyl acetal, polyvingl ether, polycarbonate and cellulose esters are more
Kind；With the weight of packaging bag film, the content of the organic additive is 0-60 weight %, preferably 10-40 weight
Measure %.
Electrode slurry presoma according to the present invention, wherein the material of the preferred packaging bag film further includes inorganic addition
Agent, the preferably described inorganic additive contain the compound of the element containing Group IIA and/or the compound containing IV A race element, preferably described
Inorganic additive is in calcium carbonate, calcium sulfate, magnesium carbonate, magnesium sulfate, calcium oxide, magnesia, carbon fiber, carbon black and white carbon black
It is one or more；More preferably with the weight of packaging bag film, the content of the inorganic additive is 1-10 weight %.
Electrode slurry presoma according to the present invention, wherein the number-average molecular weight of the preferred Kynoar is
100000-2000000。
Electrode slurry presoma according to the present invention, wherein the preferred electrode material includes electrode active material and glues
Tie agent.
Electrode slurry presoma according to the present invention, wherein the preferred electrode material includes electrode active material, conduction
Agent and binder, the conductive agent is powder or range of viscosities is 10-100Pa*s (Brookfield R/S rheometer 10s-1It is viscous
Angle value) conductive agent slurries.
Electrode slurry presoma according to the present invention, wherein electrode active material can also be with for positive active material
Use positive active material as exemplary illustration in a specific embodiment of the present invention for negative electrode active material.
Electrode slurry presoma according to the present invention, positive active material and negative electrode active material all can be this fields
Conventional selection, the present invention do not have specific requirement to its type, such as when the electrode active material is positive active material,
It can be one of LiFePO4, cobalt acid lithium, LiMn2O4 and Li-Ni-Mn-Co-O or a variety of.
Electrode slurry presoma according to the present invention, the present invention to the dosage of electrode active material without particular/special requirement, as long as
Guarantee that the electrode active material being sealed in packaging bag film can satisfy the dosage requirement of electrode slurry, does not retouch in detail herein
It states.
Electrode material can be sealed in the packaging bag film as follows by electrode slurry presoma according to the present invention
It is interior: according to stoichiometric ratio, first to control each dusty material flow using mass flowmenter, be gradually dosed in packaging bag film, then
The conductive agent of fixed amount is added, finally ties up sealing using packaging bag film rope, every part of electrode material presoma is in practical application
10-50kg。
The present invention provides a kind of electrode slurry, which passes through electrode slurry presoma of the present invention is molten
Solution obtains in organic solvent.
The present invention provides a kind of preparation methods of electrode slurry, this method comprises:
(1) it is dissolved the polymer material containing Kynoar to obtain solution using organic solvent, by the solution
It is formed a film to obtain packaging bag film；
(2) electrode material is sealed with the packaging bag film, obtains electrode slurry presoma；
(3) the electrode slurry presoma is added in organic solvent and is dissolved to obtain electrode slurry.
According to the present invention, identical technical term is described without being repeated several times, and reference is above.
Electrode slurry according to the present invention, preferred steps (3) are described to be dissolved in the presence of conductive agent slurries and carries out.
Electrode slurry according to the present invention carries out dissolution using electrode slurry presoma of the invention and prepares electrode slurry,
Feed intake more handy and safe, and more precisely, avoids wastage of material, and reduce the conveying cost of material, significantly reduce mixed
Dust pollution between truck is conducive to personnel health；And particulate electrode slurry presoma has slow releasing function, can obtain more uniform
Electrode slurries, and also avoid being mixed into for moisture and impurity, while electrode slurry viscosity is got higher by low, each component is easier
It mixes；To which the present invention can be realized the automatic charging of high viscosity component (graphene slurries, CNT slurries).
, according to the invention it is preferred to which being evaporated organic solvent in step (1) at 20 DEG C to (- 40) DEG C carries out the film forming.
According to the present invention, wherein preferred film forming carries out as follows: solution is spread in horizontal mold；At 20 DEG C
To (- 40) DEG C, evaporated under reduced pressure organic solvent.
Electrode slurry according to the present invention, the preferably dosage of the polymer material containing Kynoar are consumption of organic solvent
2-10 weight %.
The electrode slurry presoma is added in organic solvent and is dissolved to obtain electricity by electrode slurry according to the present invention
Electrode slurry presoma can for example be put into mixing tank and be mixed with organic solvent by pole slurry, stirred and evenly mixed and be slurried, through excessive
It dissipates, sieving, obtains finished electrode slurry.
According to the present invention, the condition dissolved in step (1) includes: that temperature is 20-45 DEG C.
, according to the invention it is preferred to the condition dissolved in step (1) further include: time 30-180min.
, according to the invention it is preferred to which the number-average molecular weight of the Kynoar is 100000-2000000.
, according to the invention it is preferred to the weight of the polymer material containing Kynoar, it is described to gather inclined fluorine
The content of ethylene is 40-100 weight %, preferably 60-90 weight %.
, according to the invention it is preferred to the polymer material containing Kynoar further includes organic additive, it is described organic
Additive be preferably selected from Vingon, polyvinyl alcohol, polyethylene glycol, polyacrylate, polymethacrylates, polyurethane,
One of Pioloform, polyvinyl acetal, polyvingl ether, polycarbonate and cellulose esters are a variety of.
It is described organic to add, according to the invention it is preferred to the weight of the polymer material containing Kynoar
The content for adding agent is 0-60 weight %, preferably 10-40 weight %.
, according to the invention it is preferred to the polymer material containing Kynoar further includes inorganic additive, it is described inorganic
Additive contains the compound of the element containing Group IIA and/or the compound containing IV A race element, and the more preferable inorganic additive is
One of calcium carbonate, calcium sulfate, magnesium carbonate, magnesium sulfate, calcium oxide, magnesia, carbon fiber, carbon black and white carbon black are a variety of.
It is described inorganic to add, according to the invention it is preferred to the weight of the polymer material containing Kynoar
The content for adding agent is 1-10 weight %.
, according to the invention it is preferred to which the electrode material includes electrode active material and binder, the more preferable electrode material
Material includes electrode active material, conductive agent and binder, and the preferably described conductive agent is powder or range of viscosities is 10-100Pa*s
Conductive agent slurries.
, according to the invention it is preferred to the packaging bag film with a thickness of 0.05-0.5mm, more preferably 0.1-0.3mm.
According to the present invention, the type of the binder can be the conventional selection of this field, preferably polyvinylidene fluoride
(PVDF), one of polytetrafluoroethylene (PTFE) (PTFE) and pva powder or a variety of.
According to the present invention, the dosage of the binder is preferably the 0.5-5 weight % of electrode active material quality, preferably
0.5-3 weight %.
According to the present invention, the type of the conductive agent can be this field conventional selection, such as can for conductive carbon black,
Acetylene black, electrically conductive graphite, carbon fiber, carbon nanotube slurry and graphene slurries it is one or more.
, according to the invention it is preferred to which the dosage of conductive agent is the 0.5-20 weight % of electrode active material quality.
The mixing of mixed electrode slurry composition is difficult to the invention is particularly suited to poor fluidity.
As previously mentioned, the electrode is by electrode slurry of the present invention or the present invention the present invention provides a kind of electrode
The electrode slurry of the preparation method preparation is coated on electrode current collecting body, is then dried, roll-in, cuts to obtain.
As previously mentioned, the lithium ion battery contains electrode of the present invention the present invention provides a kind of lithium ion battery.
Below by specific embodiment, the present invention is described in detail, but the present invention is not limited to this.
Embodiment 1
Packaging bag film preparation technique: 300mL beaker is taken, 25 DEG C, 190gNMP and 10g HSV900,1000rpm stirring is added
60min, obtaining concentration is 5 weight %PVDF solution；Glass bar is scratched to smooth glass pane surface；At -20 DEG C, drying is used
The dry solvent of air-blowing obtains surface density about 0.015g/cm2Thin-film material (film thickness 0.1mm)；
Electrode slurry precursor preparation technique: (proportion is shown in Table 1) is added thin after various electrode powder materials are simply mixed
In film, sealed using double-sided adhesive.
Table 1
| LiFePO4 | Super_P | HSV900 | Packaging bag film PVDF |
| 100g | 5g | 3g | 1g |
Electrode slurry preparation process are as follows: 1. put into 135gNMP in 400mL beaker；2. electrode slurry presoma is put into
In beaker, 500rpm stirs 30min；3. 1500rpm stirs 30min, scraping is shut down；4. 1500rpm stirs 90min, 200 mesh are crossed
Sieve obtains finished electrode slurry.Wherein, mixing total time is 150min.
Coating tablet making technology: 1. taking finished electrode slurry, blade coating, and substrate is Al foil, and single side piece dressing density is
160g/m2；2. drying piece parameter is 120 DEG C, 20min.
Use LiFePO4System, negative electrode tab: artificial graphite makes bag-type battery.
Comparative example 1
Charging technology are as follows: 1. put into 135gNMP in 400mL beaker；2. HSV900 is added, 1000rpm stirs 60min；
3. Super_P is added, 1000rpm is dispersed with stirring 20min；4. LiFePO4 100g is added, 1500rpm stirs 30min, and shutdown is scraped
Side；5. 1500rpm stirs 90min, crosses 200 mesh screens and obtain finished electrode slurry, wherein material amount is shown in Table 2.(mixing is total
Time is 200min).
It is coated with film-making according to the method for embodiment 1.
Table 2
| LiFePO4 | Super_P | HSV900 | NMP |
| 100g | 5g | 4g | 135g |
Embodiment 2
Electrode slurry presoma composition is shown in Table 3:
Table 3
| Li-Ni-Mn-Co-O | CNT slurries | HSV900 | Packaging bag film PVDF |
| 100g | 20g | 0 | 1g |
In CNT slurries, CNT mass fraction is 5%.
Electrode slurry preparation process are as follows: 1. put into 41gNMP in 400mL beaker；It is burnt 2. electrode slurry presoma is put into
In cup, 500rpm stirs 30min；3. 1500rpm stirs 30min, scraping is shut down；4. 1500rpm stirs 90min, 200 meshes are crossed
Net obtains finished electrode slurry.(mixing total time is 150min).
It is coated with film-making according to the method for embodiment 1 and prepares battery.
Comparative example 2
Charging technology are as follows: 1. put into 41gNMP in 400mL beaker；2. HSV900 is added, 1000rpm stirs 60min；③
CNT slurries are added, 1000rpm is dispersed with stirring 20min；4. Li-Ni-Mn-Co-O 100g is added, 1500rpm stirs 30min, and shutdown is scraped
Side；5. 1500rpm stirs 90min, manual 200 mesh screen of mistake obtains finished electrode slurry, and wherein material amount is shown in Table 4.It is (mixed
Material total time is 200min).
It is coated with film-making according to the method for embodiment 1.
Table 4
| Li-Ni-Mn-Co-O | CNT slurries | HSV900 | NMP |
| 100g | 20g | 1g | 41g |
In CNT slurries, CNT mass fraction is 5%.
Embodiment 3
The step of according to embodiment 1, prepares composite package bag film using two kinds of binder materials, remaining step is all the same,
Wherein, composite package bag film preparation technique includes: to take 300mL beaker, and 25 DEG C, 190gNMP and 9g HSV900 and the poly- second of 1g is added
Glycol (number-average molecular weight about 420,000), 1000rpm stir 60min, and obtaining concentration is 5 weight % solution；Glass bar scratch to
Smooth glass pane surface；At -20 DEG C, using the dry dry solvent of air-blowing, surface density about 0.015g/cm is obtained2Thin-film material
(film thickness 0.1mm).
Embodiment 4
The step of according to embodiment 1, prepares packaging bag film according to following step, remaining step is all the same, packaging bag film system
Standby technique: 300mL beaker is taken, 25 DEG C, 190gNMP and 10g HSV900 is added, 1000rpm stirs 60min, and obtaining concentration is 5
Weight %PVDF solution；Glass bar is scratched to smooth glass pane surface；At 120 DEG C, forced air drying 120min removes solvent,
Obtain surface density about 0.015g/cm2Thin-film material (film thickness 0.1mm).
Embodiment 5
The step of according to embodiment 1, prepares packaging bag film according to following step, remaining step is all the same:
25 DEG C, 300mL beaker is taken, 120gNMP, 70g acetone, 10g HSV900,1000rpm stirring 60min is added, obtains
5 weight %PVDF solution；Weigh 1g MgCO3Powder is put into above-mentioned solution, and 1000rpm stirs 60min；Glass bar scratch to
Smooth glass pane surface, anhydrous ethanol elution remove solvent, and room temperature is dried, and obtain surface density about 0.01g/cm2Film material
Expect (film thickness 0.1mm).
Embodiment 6
The step of according to embodiment 1, prepares packaging bag film according to following step, remaining step is all the same:
25 DEG C, 300mL beaker is taken, 120gNMP, 70g acetone, 10g HSV900,1000rpm stirring 60min is added, obtains
5 weight %PVDF solution；1g MgO powder is weighed, is put into above-mentioned solution, 1000rpm stirs 60min；Glass bar is scratched to flat
Whole glass pane surface, anhydrous ethanol elution remove solvent, and room temperature is dried, and obtain surface density about 0.01g/cm2Thin-film material
(film thickness 0.1mm).
Embodiment 7
The step of according to embodiment 1, prepares packaging bag film according to following step, remaining step is all the same:
25 DEG C, 300mL beaker is taken, 120g NMP, 70g acetone, 10g HSV900,1000rpm stirring 60min is added, obtains
To 5%PVDF solution；1g carbon fiber is weighed, is put into above-mentioned solution, 1000rpm stirs 60min；Glass bar is scratched to smooth
Glass pane surface, anhydrous ethanol elution remove solvent, and room temperature is dried, and obtain surface density about 0.01g/cm2Thin-film material (film thickness
For 0.1mm).
Test case
According to sieving time and sieve residue, electrode slurry viscosity, pole piece state, pole piece distribution of resistance, pole piece
Five test indexs of peel strength, judge electrode slurry uniform component distribution
According to solute effect, judge packaging bag film can twice dispersing in electrode slurry.
1. be sieved time and the test of screen surface residue
Recording electrode slurry is sieved the time, and visual sieve (200 mesh) surface whether there is obvious particle.
1 test result of embodiment are as follows: sieving time 15min, without obvious residue and particle
1 test result of comparative example are as follows: sieving time 18min, without obvious residue and particle
It can be seen that using electrode slurry presoma of the invention, packaging bag film can be fully dispersed in electrode slurry；
Secondary agglomeration grain diameter is smaller in electrode slurry, illustrates that each component distribution is more uniform.
2. electrode slurry viscosity test
Using Brookfield R/S rheometer, CC25 rotor observes the 10s of electrode slurry-1Viscosity.
1 test result of embodiment are as follows: 5800mPa*s
1 test result of comparative example are as follows: 6790mPa*s
2 test result of embodiment are as follows: 4850mPa*s
2 test result of comparative example are as follows: 4930mPa*s
3. pole piece state verification
Visual pole piece whether there is obvious shortcoming (scribing line/stomata/salient point etc.).
1 test result of embodiment are as follows: no significant defect
1 test result of comparative example are as follows: 3, stomata
2 test result of embodiment are as follows: no significant defect
2 test result of comparative example are as follows: no significant defect
4. pole piece resistance test
Using tetra- probe instrument of RTS-8, pole piece resistivity and distribution are detected.
1 test result of embodiment are as follows: 18 Ω * cm, unevenness 12%
1 test result of comparative example are as follows: 20 Ω * cm, unevenness 18%
2 test result of embodiment are as follows: 23 Ω * cm, unevenness 6.5%
2 test result of comparative example are as follows: 23 Ω * cm, unevenness 10.6%
It can be seen that using capsule shape electrode slurry presoma of the invention, conductive agent is distributed more in electrode slurry
Uniformly.
5. pole piece peel test force
Using electronic universal tester (rate of 50mm/min), the mechanical adhesion between pole piece dressing and collector is detected
Power.
1 test result of embodiment are as follows: 0.45N
1 test result of comparative example are as follows: 0.42N
2 test result of embodiment are as follows: 0.76N
2 test result of comparative example are as follows: 0.76N
It can be seen that preparing electrode slurry using electrode slurry presoma dissolution of the invention, binder can sufficiently dissolve
It is scattered in electrode slurry.
6. solute effect
Packaging bag film 0.5g prepared by each embodiment, adds in 100g N-Methyl pyrrolidone, 500rpm stirring
60min, observation packaging bag film dissolve dispersity again.
1 test result of embodiment are as follows: be completely dissolved dispersion
3 test result of embodiment are as follows: be completely dissolved dispersion
4 test result of embodiment are as follows: substantially insoluble
It can be seen that the packaging bag film of the method according to the invention preparation, can dissolve again and be scattered in electrode slurry.
7. judging inorganic additive solubilization-aid effect according to film layer rate of dissolution
Packaging bag film 0.5g prepared by each embodiment, adds in 100g N-Methyl pyrrolidone, 500rpm stirring
60min, detection packaging bag film are completely dissolved required time.
Embodiment 1, dissolution time 50min；
Embodiment 5, dissolution time 43min；
Embodiment 6, dissolution time 45min；
Embodiment 7, dissolution time 41min；
It can be seen that addition inorganic additive has good dissolution assistant effect.
8. judging inorganic additive effect according to 100 normal temperature circulation capacity retention ratios of battery
It tests cycle performance of battery: at 20 DEG C of room temperature, 1C charge and discharge 100 times, collecting 100 circulation volumes of battery and keep
Rate:
Embodiment 1, capacity retention ratio 89%；
Embodiment 5, capacity retention ratio 92%；
Embodiment 6, capacity retention ratio 90%.
It can be seen that addition MgCO3Battery capacity conservation rate can be improved, and effect is better than MgO.
9. determining film to HF adsorption effect, initial electrolysis liquid (six according to HF content in the electrolyte system after 48h is shelved
Lithium fluophosphate 1mol/L, solvent DMC:DEC:EMC=1:1:1, HF content are 1000wppm).
Embodiment 6 (loads 0.5g packaging bag film) in bottle: 576wppm
Comparative example (blank bottle): 1123wppm
It can be seen that MgO has the effect of absorption HF.
10. judging to add whether carbon fiber helps to improve film tensile strength according to tensiometer registration
The film for cutting fixed length and width, is stretched using electronic tensile machine, pulling force when test film is broken
Embodiment 1, pulling force registration are 1.1N；
Embodiment 7, pulling force registration are 1.5N.
It can be seen that addition carbon fiber improves film tensile strength.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (35)
1. a kind of electrode slurry presoma, which is characterized in that the electrode slurry presoma includes packaging bag film and is sealed in
Electrode material in the packaging bag film, the packaging bag film dissolve in organic solvent；Wherein, the material packet of the packaging bag film
Kynoar is included, with the weight of packaging bag film, the content of the Kynoar is 40-90 weight %, institute
The material for stating packaging bag film further includes organic additive, and the organic additive is selected from polyvinyl alcohol, polyethylene glycol, polyacrylic acid
One of ester, polyurethane, Pioloform, polyvinyl acetal, polyvingl ether, polycarbonate and cellulose esters are a variety of；With packaging bag film
Weight, the content of the organic additive is 10-60 weight %；The organic solvent is N- crassitude
Ketone, main chain are no more than in ketone, dimethyl sulfoxide, dimethylformamide, dimethyl acetamide and the tetrahydrofuran of 6 carbon atoms
It is one or more.
2. electrode slurry presoma according to claim 1, wherein the organic additive is polymethacrylates.
3. electrode slurry presoma according to claim 1, wherein the electrode material in the packaging bag film is powdered
Or paste；The packaging bag film with a thickness of 0.05-0.5mm.
4. electrode slurry presoma according to claim 3, wherein the packaging bag film with a thickness of 0.1-0.3mm.
5. electrode slurry presoma according to claim 1, wherein described with the weight of packaging bag film
The content of Kynoar is 60-90 weight %.
6. electrode slurry presoma according to claim 5, wherein described with the weight of packaging bag film
The content of organic additive is 10-40 weight %.
7. electrode slurry presoma according to claim 1, wherein the material of the packaging bag film further includes inorganic addition
Agent, the inorganic additive contain the compound of the element containing Group IIA and/or the compound containing IV A race element；The packaging bag film
The sum of each component content percentage be 100%.
8. electrode slurry presoma according to claim 7, wherein the inorganic additive is calcium carbonate, calcium sulfate, carbon
One of sour magnesium, magnesium sulfate, calcium oxide and magnesia are a variety of.
9. electrode slurry presoma according to claim 1, wherein the material of the packaging bag film further includes inorganic addition
Agent, the inorganic additive are white carbon black, and the sum of each component content percentage of the packaging bag film is 100%.
10. electrode slurry presoma according to claim 1, wherein the material of the packaging bag film further includes inorganic adds
Add agent, the inorganic additive includes carbon fiber and/or carbon black, and the sum of each component content percentage of the packaging bag film is
100%.
11. electrode slurry presoma according to claim 8, wherein described with the weight of packaging bag film
The content of inorganic additive is 1-10 weight %.
12. electrode slurry presoma according to claim 9 or 10, wherein with the weight of packaging bag film,
The content of the inorganic additive is 1-10 weight %.
13. electrode slurry presoma according to claim 1, wherein the number-average molecular weight of the Kynoar is
100000-2000000。
14. electrode slurry presoma according to claim 1, wherein the electrode material include electrode active material and
Binder.
15. electrode slurry presoma according to claim 14, wherein the electrode material include electrode active material,
Conductive agent and binder.
16. electrode slurry presoma according to claim 15, wherein the conductive agent is powder or range of viscosities is
The conductive agent slurries of 10-100Pa*s.
17. a kind of electrode slurry, which is characterized in that the electrode slurry is by by electricity described in any one of claim 1-16
Slurry presoma dissolution in pole obtains in organic solvent.
18. a kind of preparation method of electrode slurry, which is characterized in that this method comprises:
(1) it is dissolved the polymer material containing Kynoar to obtain solution using organic solvent, the solution is carried out
Film forming obtains packaging bag film；
(2) electrode material is sealed with the packaging bag film, obtains electrode slurry presoma；
(3) the electrode slurry presoma is added in organic solvent and is dissolved to obtain electrode slurry, wherein gather inclined fluorine to contain
The weight of the polymer material of ethylene, the content of the Kynoar are 40-90 weight %；It is described inclined containing gathering
The polymer material of vinyl fluoride further includes organic additive, and the organic additive is selected from polyvinyl alcohol, polyethylene glycol, polypropylene
One of acid esters, polyurethane, Pioloform, polyvinyl acetal, polyvingl ether, polycarbonate and cellulose esters are a variety of；Containing poly- inclined
The weight of the polymer material of vinyl fluoride, the content of the organic additive are 10-60 weight %；It is described organic
Solvent is N-Methyl pyrrolidone, main chain is no more than ketone, dimethyl sulfoxide, the dimethylformamide, dimethyl second of 6 carbon atoms
One of amide and tetrahydrofuran are a variety of.
19. preparation method according to claim 18, wherein the organic additive is polymethacrylates.
20. preparation method according to claim 18, wherein be evaporated at 20 DEG C to subzero 40 DEG C in step (1) organic
Solvent carries out the film forming.
21. preparation method according to claim 18, wherein the condition dissolved in step (1) includes: that temperature is 20-45
DEG C, time 30-180min, the dosage of the polymer material containing Kynoar is the 2-10 weight % of consumption of organic solvent；
Step (3) is described to be dissolved in the presence of conductive agent slurries and carries out；The number-average molecular weight of the Kynoar is 100000-
2000000。
22. preparation method according to claim 21, wherein with the weight percent of the polymer material containing Kynoar
Content meter, the content of the Kynoar are 60-90 weight %.
23. preparation method according to claim 22, wherein with the weight percent of the polymer material containing Kynoar
Content meter, the content of the organic additive are 10-40 weight %.
24. preparation method according to claim 21, wherein the polymer material containing Kynoar further includes nothing
Machine additive, the inorganic additive contain the compound of the element containing Group IIA and/or the compound containing IV A race element；It is described to contain
The sum of each component content percentage of the polymer material of Kynoar is 100%.
25. preparation method according to claim 24, wherein the inorganic additive is calcium carbonate, calcium sulfate, carbonic acid
One of magnesium, magnesium sulfate, calcium oxide and magnesia are a variety of.
26. preparation method according to claim 18, wherein the polymer material containing Kynoar further includes nothing
Machine additive, the inorganic additive are white carbon black, each component content percentage of the polymer material containing Kynoar
The sum of number is 100%.
27. preparation method according to claim 18, wherein the polymer material containing Kynoar further includes nothing
Machine additive, the inorganic additive include carbon fiber and/or carbon black, each group of the polymer material containing Kynoar
Dividing the sum of content percentage is 100%.
28. preparation method according to claim 25, wherein with the weight percent of the polymer material containing Kynoar
Content meter, the content of the inorganic additive are 1-10 weight %.
29. the preparation method according to claim 26 or 27, wherein with the weight of the polymer material containing Kynoar
Percentage composition meter, the content of the inorganic additive are 1-10 weight %.
30. preparation method according to claim 21, wherein the electrode material includes electrode active material and bonding
Agent.
31. preparation method according to claim 30, wherein the electrode material includes electrode active material, conductive agent
And binder, the conductive agent slurries that the conductive agent is powder or range of viscosities is 10-100Pa*s.
32. preparation method according to claim 30, wherein the packaging bag film with a thickness of 0.05-0.5mm.
33. preparation method according to claim 32, wherein the packaging bag film with a thickness of 0.1-0.3mm.
34. a kind of electrode, which is characterized in that electrode electrode slurry as described in claim 17 or claim 18-33
Any one of described in preparation method preparation electrode slurry be coated in electrode current collecting body on, then dried, roll-in and
It cuts to obtain.
35. a kind of lithium ion battery, which is characterized in that the lithium ion battery contains electrode described in claim 34.
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| CN106684316A (en) * | 2017-01-16 | 2017-05-17 | 赵社涛 | Clean pulping method of cathode material for lithium ion battery |
| CN106711398A (en) * | 2017-01-16 | 2017-05-24 | 赵社涛 | Clean pulping method for conductive agent material of chemical power supply |
| CN106711404A (en) * | 2017-01-16 | 2017-05-24 | 赵社涛 | Clean pulping method for lithium ion battery cathode material |
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| CN102487141A (en) * | 2010-12-02 | 2012-06-06 | 比亚迪股份有限公司 | Cathode material of lithium ion battery and battery |
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| CN102487141A (en) * | 2010-12-02 | 2012-06-06 | 比亚迪股份有限公司 | Cathode material of lithium ion battery and battery |
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