CN108417837A - A kind of aqueous polyimide adhesive of Anode of lithium cell material and preparation method - Google Patents
A kind of aqueous polyimide adhesive of Anode of lithium cell material and preparation method Download PDFInfo
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- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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Abstract
The invention discloses a kind of aqueous polyimide adhesives of Anode of lithium cell material and preparation method thereof, including：(1) under inert atmosphere, reactant is added into reaction kettle, is warming up to solid and is completely dissolved；(2) catalyst is added, temperature reaction to no carbon dioxide is released；It is cooling, it is blended into solvent after weighing；(3) it filters to get filtrate；(4) solution that step (3) obtains is weighed, dodecyl benzene sulfonic acid lithium solution is added dropwise thereto, is stirred；(5) mixed liquor that step (4) obtains is warming up to 65 85 DEG C, deionized water is added dropwise；(6) mixed liquor that step (5) obtains is weighed, deionized water is added；(7) solution, LiFePO 4 and graphene that step (6) obtains are weighed, LiFePO 4, graphene are sequentially added in solution, after mixing, deionized water is added and adjusts viscosity, the advantage of the invention is that, influence of the bonding agent to anode material capacitance is reduced, while reducing the usage amount of organic solvent, reduces pollution.
Description
Technical field
The invention belongs to telephoning telephony technical fields, and in particular to a kind of aqueous polyimide adhesive of Anode of lithium cell material
And preparation method.
Background technology
The survival and development of the energy and human society are closely bound up, and sustainable development is the common hope of all mankind and put forth energy
Struggle against target.In order to realize sustainable development, it is necessary to protect natural environment and natural resources for the survival of mankind.Ministry of Industry and Information is directed to
Some countries have formulated the timetable for stopping production and sales traditional energy automobile, also start formulate China's stopping life at present
The timetable of traditional energy automobile is sold in production and marketing.New energy and new energy materials are the important sets for completing this world-class very important decision
At part..
As the accumulator of energy storage device, it is widely used in the production of the mankind and life, but with
The requirements at the higher level of electric vehicle, mechanics of communication and the rapid development of the industrialization of information and current environmental protection, this
Allow for exploitation a new generation produce and using process it is all pollution-free, have high-energy density, high power density, security performance
One of important goal good, cycle charge discharge electrical property is good, relatively low cost New Green Battery develops as new energy field.
Compared with conventional batteries, secondary lithium battery is high with operating voltage, bigger than energy, charge discharge life is long, certainly
The advantages that discharge rate is low, good cycle.Secondary lithium battery currently on the market, positive electrode used substantially have four
Major class：The violent oxygen positive electrode (LiMn2O4) of lithium nickel oxygen positive electrode (LiNiO2), lithium, lithium oxygen plus plate material (LiCoO2) and
Lithium iron phosphate cathode material (LiFePO4) of latest development needs these materials being made micro- during anode production
Then meter level is bonded in binder on anode thin slice to Subnano-class particle, anode use is further made.
Existing binder has two major classes, when solvent type vinylidene chloride binder, wherein organic molten containing 65-80%
Agent, these organic solvents are：NN- dimethyl pyrrolidones, NN- dimethylformamides, NN dimethylacetylamides and aldehyde, ketone
Equal organic solvents have serious harm during binder and anode pole piece to direct labor's body, and in product drying
A large amount of organic solvent is diffused into air in the process, causes seriously to pollute；Second is that aqueous gelatin binder, due to gelatin sheet
Body cohesive force, toughness are bad, so needing to add styrene-butadiene latex, increase toughness；It adds polyoxyethylene and increases cohesive force, add carbon
Powder increases conductivity.And the addition of additive, cause the capacitance of anode material to be greatly lowered.
Invention content
Technical problem to be solved by the present invention lies in：Various additives, which are added, in existing aqueous gelatin bonding agent leads to sun
Pole material capacitance reduces.
The present invention solves above-mentioned technical problem using following technical scheme：
A kind of preparation method of the aqueous polyimide adhesive of Anode of lithium cell material, includes the following steps：(1) inertia
Under atmosphere, NN- dimethylacetylamides, dibasic acid anhydride and isophorone diisocyanate, heating systems temperature are added into reaction kettle
Degree is to 50-60 DEG C, until solid is completely dissolved；The molar ratio of the dibasic acid anhydride and diisocyanate is 1:1；
(2) organic silver catalyst is added into reaction kettle, temperature reaction to no carbon dioxide stops when releasing；It is cooled to
60-80 DEG C, NN- dimethylacetylamides are blended into after weighing；
(3) it is 14%-16% polyimide resin solutions that solid content, which is obtained by filtration,；
(4) polyimide resin solution that step (3) obtains is weighed, dodecyl benzene sulfonic acid lithium solution is added dropwise thereto,
It is stirred, a concentration of 35-40% of the dodecyl benzene sulfonic acid lithium solution, PH 12-12.5；Dodecyl benzene sulfonic acid lithium
The dosage of solution is the 15%-18% of polyimide resin solution.
(5) mixed liquor that step (4) obtains is warming up to 65-85 DEG C, deionized water is added dropwise while agitating；
(6) mixed liquor that step (5) obtains is weighed, deionized water is added in stirring while, and it is 1%-2% to obtain solid content
Polyimide transparent solution；
(7) solution, LiFePO 4 and graphene that step (6) obtains, polyimide resin, ferrous phosphate are weighed respectively
The mass ratio of lithium and graphene is 2：98：4.9, LiFePO 4 is added in solution, and is stirred evenly；Graphene is added,
After mixing, deionized water is added and adjusts viscosity.
Preferably, the preparation method of a kind of aqueous polyimide adhesive of Anode of lithium cell material of the present invention, institute
It states dibasic acid anhydride and is selected from 1,2,4,5- cyclohexanetetracarboxylic acids dianhydride, pyromellitic acid anhydride, diphenyl ether tetraformic dianhydride.
Preferably, the preparation method of a kind of aqueous polyimide adhesive of Anode of lithium cell material of the present invention, institute
It is 1,2,4,5- cyclohexanetetracarboxylic acid dianhydrides to state dibasic acid anhydride.
Preferably, the preparation method of a kind of aqueous polyimide adhesive of Anode of lithium cell material of the present invention, institute
State the 0.3%-0.4% that the organic silver catalyst amount being added in step (2) is dibasic acid anhydride quality.
Preferably, the preparation method of a kind of aqueous polyimide adhesive of Anode of lithium cell material of the present invention, institute
It is CAT-100E to state the organic silver catalyst being added in step (2).
Preferably, the preparation method of a kind of aqueous polyimide adhesive of Anode of lithium cell material of the present invention, institute
It states the deionized water being added in step (5) and is previously heated to 80-85 DEG C.
Preferably, the preparation method of a kind of aqueous polyimide adhesive of Anode of lithium cell material of the present invention, institute
The amount for stating the deionized water of step (5) addition is the 125% of polyimide resin solution quality.
Preferably, the preparation method of a kind of aqueous polyimide adhesive of Anode of lithium cell material of the present invention, institute
The Adding Way for stating LiFePO 4 in step (7) is:LiFePO 4 is divided into five equal portions, sequentially adds solution, every time
It is stirred and evenly mixed after addition.
Preferably, the preparation method of the aqueous polyimide adhesive of the material of Anode of lithium cell always of the present invention, institute
The Adding Way for stating graphene in step (7) is：Graphene is divided into five equal portions, sequentially adds solution, is stirred after being added every time
Mix mixing.
The present invention also provides a kind of aqueous polyimide adhesives of Anode of lithium cell material, by a kind of above-mentioned lithium electricity
The preparation method of the aqueous polyimide adhesive of pond anode material is prepared.
The technology of the present invention advantageous effect：
The technology of the present invention side enhances toughness using isophorone diisocyanate synthesis of polyimides, while having good
Aqueous affinity, thus deionized water can be used to replace organic solvent, substantially reduce the harm to human body and environment；Using having
Machine silver catalyst, dosage is few, environmental sound, and dodecyl benzene sulfonic acid lithium does not have anode material as anion surfactant
There is any harmful effect, the capacitance of anode material will not be reduced, LiFePO 4 is bonded by bonding agent prepared by this method
Anode material is made ferrous phosphate lithium battery, capacitance 145-160mAh/g, and capacity retention still exists after charge and discharge 1000 times
80% or more.
Specific implementation mode
For ease of those skilled in the art understand that technical solution of the present invention, in conjunction with specific embodiment to the technology of the present invention side
Case is described further.
Technical solution of the present invention provides a kind of aqueous polyimide adhesive of Anode of lithium cell material, which passes through
Following methods are prepared：
(1) under inert atmosphere, NN- dimethylacetylamides, two isocyanide of dibasic acid anhydride and isophorone are added into reaction kettle
Acid esters, heating systems temperature is to 50-60 DEG C, until solid is completely dissolved；The molar ratio of the dibasic acid anhydride and diisocyanate is
1:1；Inert atmosphere can be generated by multiple gases, such as nitrogen, rare gas, and the present embodiment is preferably nitrogen；The binary
Acid anhydrides be selected from 1,2,4,5- cyclohexanetetracarboxylic acid dianhydrides, pyromellitic acid anhydride, diphenyl ether tetraformic dianhydride, preferably 1,2,4,
5- cyclohexanetetracarboxylic acid dianhydrides.
(2) organic silver catalyst CAT-100E of dibasic acid anhydride quality 0.3%-0.4% is added into reaction kettle, is warming up to
130-185 DEG C, until stopping reaction when being released without carbon dioxide；It is cooled to 60-80 DEG C, NN- dimethylacetylamides are blended into after weighing；
(3) it is 14%-16% polyimide resin solutions that solid content, which is obtained by filtration,；
(4) polyimide resin solution that step (3) obtains is weighed, dodecyl benzene sulfonic acid lithium solution is added dropwise thereto,
It is stirred, a concentration of 35-40% of the dodecyl benzene sulfonic acid lithium solution, PH 12-12.5；Dodecyl benzene sulfonic acid lithium
The dosage of solution is the 15%-18% of polyimide resin solution.
The preparation method of dodecyl benzene sulfonic acid lithium is：It weighs dodecyl benzene sulfonic acid lithium (technical pure) and deionized water is added
In, stirring and dissolving；Lithium hydroxide (technical pure) stirring and dissolving is added into solution, until PH stablizes in 12-12.5.
(5) mixed liquor that step (4) obtains is warming up to 65-85 DEG C, is added dropwise is preheated to 80- in advance while agitating
85 DEG C of deionized water, the amount of the deionized water of addition are the 125% of polyimide resin solution quality.
(6) mixed liquor that step (5) obtains is weighed, deionized water is added in stirring while, and it is 1%-2% to obtain solid content
Polyimide transparent solution；
(7) solution, LiFePO 4 and graphene that step (6) obtains, polyimide resin, ferrous phosphate are weighed respectively
The mass ratio of lithium and graphene is 2：98：4.9, LiFePO 4 is divided into five equal portions, sequentially adds solution, after being added every time
It stirs and evenly mixs；Graphene is divided into five equal portions again, sequentially adds solution, is stirred and evenly mixed after being added every time；Be eventually adding from
The requirement that sub- water adjustment viscosity complies with coating machine obtains product.
Embodiment 1
(1) N of high-purity is passed through into glass reaction kettle2, NN- dimethylacetamide solvents are added into reaction kettle
1500g, 1,2,4,5- cyclohexanetetracarboxylic acid dianhydride 313.84g and isophorone diisocyanate 311.21g, are warming up to 50 DEG C,
Solid is completely dissolved；NN- dimethylacetamide solvents first pass through molecular sieve water removal in advance；
(2) catalyst CAT-100E1.00g is added into system, after being warming up to 130 DEG C, system releases carbon dioxide, after
Continuous temperature reaction, up to no carbon dioxide is released, system temperature is 180 degrees Celsius at this time；NN- dimethylacetamides are blended into after weighing
Amine；
(3) when system temperature drops to 80 DEG C, the 1 of pale yellow transparent is obtained by filtration, 2,4,5- hexamethylene, four formyl is different
Phorone imide liquor, the solid content of solution is 15% at this time；
(4) dodecyl benzene sulfonic acid lithium solution is prepared, the solution 100.00g that step (3) obtains is weighed, is added into the solution
Enter 17.00g dodecyl benzene sulfonic acid lithium solution, is sufficiently stirred；
(5) solution that step (4) obtains is heated to 80 DEG C, deionized water 124.41g, the deionization is added dropwise while stirring
Water is pre-heated to 80 DEG C；The solid content of solution is 6.21% at this time；
(6) the solution 100g that step (5) obtains is weighed, 450g deionized waters are added while stirring, obtains consolidating for solution and contains
Amount is 1.13%；
(7) solution 100g, LiFePO 4 micro mist 55.37g, graphene 2.77g that step (6) obtains are weighed, by phosphoric acid
Ferrous lithium is divided into five equal portions, is added sequentially in solution, and 25-30min is stirred after being added every time；Graphene is divided into five again
Equal portions are added sequentially in mixture, and 25-30min is stirred after being added every time, and last time stir 2.5 hours to mixing after being added
It closes uniformly, is eventually adding deionized water adjustment viscosity, complies with coating and require.
It prepares ferrous phosphate lithium battery and tests, the specific method is as follows：
Prepare battery：By positive electrode LiFeO4It is sufficiently mixed with bonding agent obtained, and is uniformly coated on fluid aluminium foil
On, dry back roller is depressed into thickness and is the thin slice of 0.07mm-0.08mm, then strikes out the former piece of a diameter of 13.5mm, obtains anode
Piece dries positive plate in 120 DEG C of drying box；Cathode uses high purity metal lithium piece；Battery assembles under an argon atmosphere
It is compacted afterwards with sealing machine.
Test：Use the capacitance of cell tester detection battery for 150mAh/g, battery after multiple cycle charge-discharge
The rate of decay is obviously low compared with conventional batteries, and cycle charge-discharge number increases considerably.
Embodiment 2
(1) N of high-purity is passed through into glass reaction kettle2, NN- dimethylacetamide solvents are added into reaction kettle
1500g, pyromellitic acid anhydride 305.27g and isophorone diisocyanate 311.21g, are warming up to 55 DEG C, solid is completely molten
Solution；NN- dimethylacetamide solvents first pass through molecular sieve water removal in advance；
(2) catalyst CAT-100E1.07g is added into system, after being warming up to 130 DEG C, system releases carbon dioxide, after
Continuous temperature reaction, up to no carbon dioxide is released, system temperature is 176 DEG C at this time；NN- dimethylacetylamides are blended into after weighing；
(3) when system temperature drops to 60 DEG C, the four formyl isophorone imines of equal benzene that amber transparent is obtained by filtration is molten
Liquid, the solid content of solution is 14% at this time；
(4) dodecyl benzene sulfonic acid lithium solution is prepared, the solution 100.00g that step (3) obtains is weighed, is added into the solution
Enter 15.00g dodecyl benzene sulfonic acid lithium solution, is sufficiently stirred；
(5) solution that step (4) obtains is heated to 85 DEG C, deionized water 124.41g, the deionization is added dropwise while stirring
Water is pre-heated to 85 DEG C；The solid content of solution is 5.61% at this time；
(6) the solution 100g that step (5) obtains is weighed, 350g deionized waters are added while stirring, obtains consolidating for solution and contains
Amount is 1.25%；
(7) solution 100g, LiFePO 4 micro mist 71.05g, graphene 3.55g that step (6) obtains are weighed, by phosphoric acid
Ferrous lithium is divided into five equal portions, is added sequentially in solution, and 25-30min is stirred after being added every time；Graphene is divided into five again
Equal portions are added sequentially in mixture, and 25-30min is stirred after being added every time, and last time is stirred 3 hours after being added and extremely mixed
Uniformly, it is eventually adding deionized water adjustment viscosity, coating is complied with and requires.
It prepares ferrous phosphate lithium battery and tests, the specific method is as follows：
Prepare battery：By positive electrode LiFeO4It is sufficiently mixed with bonding agent obtained, and is uniformly coated on fluid aluminium foil
On, dry back roller is depressed into thickness and is the thin slice of 0.07mm-0.08mm, then strikes out the former piece of a diameter of 13.5mm, obtains anode
Piece dries positive plate in 120 DEG C of drying box；Cathode uses high purity metal lithium piece；Battery assembles under an argon atmosphere
It is compacted afterwards with sealing machine.
Test：Use the capacitance of cell tester detection battery for 160mAh/g, battery after multiple cycle charge-discharge
The rate of decay is obviously low compared with conventional batteries, and cycle charge-discharge number increases considerably.
Embodiment 3
(1) N of high-purity is passed through into glass reaction kettle2, NN- dimethylacetamide solvents are added into reaction kettle
1500g, dimethyl ether tetracarboxylic acid dianhydride 434.29g and isophorone diisocyanate 311.21g, are warming up to 50 DEG C, solid is complete
Dissolving；NN- dimethylacetamide solvents first pass through molecular sieve water removal in advance；
(2) catalyst CAT-100E1.74g is added into system, after being warming up to 130 DEG C, system releases carbon dioxide, after
Continuous temperature reaction, up to no carbon dioxide is released, system temperature is 184 DEG C at this time；NN- dimethylacetylamides are blended into after weighing；
(3) when system temperature drops to 70 DEG C, the transparent four formyl isophorone of dimethyl ether of sepia color is obtained by filtration
Imide liquor, the solid content of solution is 16% at this time；
(4) dodecyl benzene sulfonic acid lithium solution is prepared, the solution 100.00g that step (3) obtains is weighed, is added into the solution
Enter 18.00g, is sufficiently stirred；
(5) solution that step (4) obtains is heated to 85 DEG C, deionized water 124.41g, the deionization is added dropwise while stirring
Water is pre-heated to 80 DEG C；The solid content of solution is 6.60% at this time；
(6) the solution 100g that step (5) obtains is weighed, 234g deionized waters are added while stirring, obtains consolidating for solution and contains
Amount is 1.98%；
(7) solution 100g, LiFePO 4 micro mist 97.22g, graphene 4.86g that step (6) obtains are weighed, by phosphoric acid
Ferrous lithium is divided into five equal portions, is added sequentially in solution, and 25-30min is stirred after being added every time；Graphene is divided into five again
Equal portions are added sequentially in mixture, and 25-30min is stirred after being added every time, and last time is stirred 3 hours after being added and extremely mixed
Uniformly, it is eventually adding deionized water adjustment viscosity, coating is complied with and requires.
It prepares ferrous phosphate lithium battery and tests, the specific method is as follows：
Prepare battery：By positive electrode LiFeO4It is sufficiently mixed with bonding agent obtained, and is uniformly coated on fluid aluminium foil
On, dry back roller is depressed into thickness and is the thin slice of 0.07mm-0.08mm, then strikes out the former piece of a diameter of 13.5mm, obtains anode
Piece dries positive plate in 120 DEG C of drying box；Cathode uses high purity metal lithium piece；Battery assembles under an argon atmosphere
It is compacted afterwards with sealing machine.
Test：Use the capacitance of cell tester detection battery for 147mAh/g, battery after multiple cycle charge-discharge
The rate of decay is obviously low compared with conventional batteries, and cycle charge-discharge number increases considerably.
Technical solution of the present invention is exemplarily described invention above in conjunction with specific embodiment, it is clear that the present invention has
Body realization is not subject to the restrictions described above, as long as using the various non-realities of inventive concept and technical scheme of the present invention progress
Matter is improved, or it is not improved the design of invention and technical solution are directly applied into other occasions, the equal guarantors in the present invention
Within the scope of shield.
Claims (10)
1. a kind of preparation method of the aqueous polyimide adhesive of Anode of lithium cell material, includes the following steps：
(1) under inert atmosphere, NN- dimethylacetylamides, dibasic acid anhydride and isophorone diisocyanate are added into reaction kettle,
Heating systems temperature is to 50-60 DEG C, until solid is completely dissolved；The molar ratio of the dibasic acid anhydride and diisocyanate is 1:1；
(2) organic silver catalyst is added into reaction kettle, until temperature reaction to no carbon dioxide is released；It is cooled to 60-80 DEG C,
NN- dimethylacetylamides are blended into after weighing；
(3) it is 14%-16% polyimide resin solutions that solid content, which is obtained by filtration,；
(4) polyimide resin solution that step (3) obtains is weighed, dodecyl benzene sulfonic acid lithium solution, stirring are added dropwise thereto
Mixing, a concentration of 35-40% of the dodecyl benzene sulfonic acid lithium solution, PH 12-12.5；Dodecyl benzene sulfonic acid lithium solution
Dosage be polyimide resin solution 15%-18%.
(5) mixed liquor that step (4) obtains is warming up to 65-85 DEG C, deionized water is added dropwise while agitating；
(6) mixed liquor that step (5) obtains is weighed, deionized water is added in stirring while, and it is the poly- of 1%-2% to obtain solid content
Acid imide clear solution；
(7) weigh solution, LiFePO 4 and graphene that step (6) obtains respectively, polyimide resin, LiFePO 4 and
The mass ratio of graphene is 2：98：4.9, LiFePO 4 is added in solution, and is stirred evenly；Graphene is added, is mixed
After uniformly, deionized water is added and adjusts viscosity.
2. a kind of preparation method of aqueous polyimide adhesive of Anode of lithium cell material according to claim 1, special
Sign is that the dibasic acid anhydride is selected from 1,2,4,5- cyclohexanetetracarboxylic acid dianhydrides, pyromellitic acid anhydride, diphenyl ether tetraformic two
Acid anhydride.
3. a kind of preparation method of aqueous polyimide adhesive of Anode of lithium cell material according to claim 2, special
Sign is that the dibasic acid anhydride is 1,2,4,5- cyclohexanetetracarboxylic acid dianhydrides.
4. a kind of preparation method of aqueous polyimide adhesive of Anode of lithium cell material according to claim 1, special
Sign is that the organic silver catalyst amount being added in the step (2) is the 0.3%-0.4% of dibasic acid anhydride quality.
5. a kind of preparation method of aqueous polyimide adhesive of Anode of lithium cell material according to claim 1 or 4,
It is characterized in that, the organic silver catalyst being added in the step (2) is CAT-100E.
6. a kind of preparation method of aqueous polyimide adhesive of Anode of lithium cell material according to claim 1, special
Sign is that the deionized water being added in the step (5) is previously heated to 80-85 DEG C.
7. a kind of preparation method of aqueous polyimide adhesive of Anode of lithium cell material according to claim 1 or 6,
It is characterized in that, the amount for the deionized water that the step (5) is added is the 125% of polyimide resin solution quality.
8. a kind of preparation method of aqueous polyimide adhesive of Anode of lithium cell material according to claim 1, special
Sign is that the Adding Way of LiFePO 4 is in the step (7):LiFePO 4 is divided into five equal portions, is sequentially added
Solution stirs and evenly mixs after being added every time.
9. the preparation method of the aqueous polyimide adhesive of the material of Anode of lithium cell always according to claim 1 or 8,
It is characterized in that, the Adding Way of graphene is in the step (7)：Graphene is divided into five equal portions, sequentially adds solution, often
It is stirred and evenly mixed after secondary addition.
10. a kind of aqueous polyimide adhesive of Anode of lithium cell material, by a kind of lithium of claim 1-9 any one of them
The preparation method of the aqueous polyimide adhesive of battery anode material is prepared.
Priority Applications (1)
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