CN104327762A - Enhanced-type composite adhesive of lithium ion battery, preparation method and application thereof - Google Patents
Enhanced-type composite adhesive of lithium ion battery, preparation method and application thereof Download PDFInfo
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- CN104327762A CN104327762A CN201410519379.7A CN201410519379A CN104327762A CN 104327762 A CN104327762 A CN 104327762A CN 201410519379 A CN201410519379 A CN 201410519379A CN 104327762 A CN104327762 A CN 104327762A
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses an enhanced-type composite adhesive of a lithium ion battery, a preparation method and an application thereof and belongs to the technical field of lithium ion battery adhesives. In the enhanced-type composite adhesive, a carboxyl group on a carboxyl-functionalized carbon nanotube can be condensed with groups, such as a hydroxyl group and the like, in a water-soluble high-molecular compound to form a bond for forming the enhanced-type composite adhesive. The enhanced-type composite adhesive has following three advantages: (1) the enhanced-type composite adhesive is greatly enhanced in tensile strength; (2) by means of a three-dimensional electric-conductive network formed by the carbon nanotube, the enhanced-type composite adhesive is effectively improved in electric-conductivity; and (3) the enhanced-type composite adhesive contains a special functional group which can be bonded with an electrode active material and is beneficial to ion transmission and tight combination between the composite adhesive and the active material can be maintained even a large size change is generated in the active material, so that a powder-falling phenomenon caused by volume expansion during a charging and discharging process can be prevented and cycling stability of the electrode active material is improved.
Description
Technical field
The present invention relates to a kind of lithium ion battery enhancement type composite adhesive, and the preparation method and application of this composite adhesive, belong to adhesive for lithium ion battery technical field.
Background technology
Along with mancarried electronic aid with the development of electromobile, more and more higher requirement is proposed to the energy density of lithium ion battery.In order to reach the object improving lithium ion battery energy density, the critical materials such as positive pole, negative pole, barrier film and electrolytic solution all have much room for improvement.In negative pole, traditional graphite material, because of Theoretical Mass specific storage lower (375mAh/g), cannot meet the requirement of lithium ion battery of new generation.The Novel anode material of height ratio capacity is subject to the attention of numerous research staff gradually, but this type of material is deviate from often along with larger volume change at Lithium-ion embeding, easily causes active material depart from collector and cause cell container to decay.At present often adopt electrode materials nanometer, improve the charge-discharge performance of heavy body negative pole with the method such as non-active material compound.In addition, novel electrode binder also effectively can fix active material, improves the stable circulation performance of Novel anode material.And conventional tackiness agent is as N-Methyl pyrrolidone (NMP) solution of polyvinylidene difluoride (PVDF) (PVDF), active material can be fixed on a current collector preferably when being used as the tackiness agent of volume change less material, but easily there is plastic deformation as during Large Copacity material adhesive, thus make it be separated with active material.For this reason, people successively develop aqueous adhesive as starch (application number: 200380102888.X), multiple copolymer (application number: 200910193676.6) etc.But at present conventional aqueous adhesive such as carboxymethyl cellulose etc. is straight-chain molecule, its cohesive force and tensile strength limited, ion and electronic conductivity are also lower.Chinese patent (application number: 200680029579.8) disclose a kind of mixture tackiness agent comprising carbon nanotube, be made up of functionalized carbon nano-tube (as carboxyl functional group introduced end or the surface of carbon nanotube) and polymerizable material (as polymerisable monomer, oligopolymer etc.), polymkeric substance and composition thereof after light and/or thermal treatment, wherein carbon nanotube significantly can improve the mechanical property of tackiness agent, is combined securely with polymkeric substance.But because not considering the bonding force between tackiness agent and active material, its cyclical stability still has room for promotion.And the dissolving of its tackiness agent still needs with an organic solvent, can cause certain influence to environment.
Summary of the invention
The object of this invention is to provide between a kind of and active material the lithium ion battery enhancement type composite adhesive that bonding force is strong, specific conductivity is high, tensile strength is large.
Meanwhile, the present invention also provides a kind of preparation method of lithium ion battery enhancement type composite adhesive.
Finally, the invention provides the application of a kind of above-mentioned composite adhesive in lithium cell.
In order to realize above object, the technical solution adopted in the present invention is:
A kind of lithium ion battery enhancement type composite adhesive, be made up of carboxyl function carbon nano tube and the water-soluble polymer containing A, B two kinds of groups, A group is carboxyl, and B group is hydroxyl and/or amino, and the mass ratio of described carbon nanotube and water-soluble polymer is 0.1 ~ 1.
The preparation of described carboxyl function carbon nano tube can refer to patent (application number: 200680029579.8), acid treatment method is: added by the carbon nanotube accounting for solution quality 1 ~ 2% in the mixed solution of the vitriol oil and concentrated nitric acid, at 60 ~ 120 DEG C, 2 ~ 12 hours are refluxed (with shortening carbon nano-tube after ultrasonic, it is made not easily wound upon themselves to occur, and in fracture grafting the hydrophilic functional group such as carboxyl, strengthen its dispersiveness in aqueous), washing, dry.
In described mixed solution, the volume ratio of the vitriol oil and concentrated nitric acid is 3:(1 ~ 2).
Described ultrasonic parameter is: ultrasonic frequency 20 ~ 30kHz, power 450 ~ 550W, and ultrasonic time is 6 ~ 24 hours.Preferably, ultrasonic frequency 22kHz, power 500W.
Described water-soluble polymer is any one in sodium alginate, Xylo-Mucine, cm-chitosan, carboxymethyl chitin, sodium starch glycolate, or the above-mentioned cross-linked hydrogel etc. that several are formed.
A preparation method for lithium ion battery enhancement type composite adhesive, comprises the following steps: carboxyl function carbon nano tube and water-soluble polymer are added to the water, mix.
The application of lithium ion battery enhancement type composite adhesive in lithium cell, wherein composite adhesive is as the required component of negative pole, and its consumption is 20 ~ 50% of negative active core-shell material quality.
Described negative active core-shell material comprises carbon class, silicon class, tin class and matrix material (as silicon-carbon, silicon-tin composite material) thereof.Carbon class active material mainly contains graphite-like (as natural graphite, electrographite), non-graphite (as MCMB, biomass charcoal) and carbon nanomaterial.Silicon class active material comprises silicon monomer (have crystal and amorphous), nano-silicon (spherical or linear), silicon-carbon mixture, Si oxide (as SiO
0.8, SiO
1.1), silicon alloy (as Li-Si, Mn-Si, Al-Si) etc.Tin class active material comprises tin-based oxide, tin-based alloy, tin carbon complex (as tin cobalt carbon composite amorphous material) etc.
In lithium cell, electrode materials is except comprising negative active core-shell material, composite adhesive, and also containing conductive agent, the consumption of conductive agent is 10 ~ 50% of negative active core-shell material quality.
Described conductive agent comprises carbon nanotube, superconduction carbon black, high electric conductivity carbon, carbon fiber, Ketjen black, Graphene, metal nano fiber (as copper nanofiber, nickel nanofiber) etc.
Beneficial effect of the present invention:
Carboxyl in the present invention on carboxyl function carbon nano tube can with the groups condense Cheng Jian such as the hydroxyl in water-soluble polymer, form enhancement type composite adhesive.This composite adhesive has the advantage of following three aspects: one, the tensile strength of binding agent strengthens greatly; Two, the three-dimensional conductive network that carbon nanotube is formed effectively can improve the electroconductibility of composite adhesive; Three, there is chemical bonding effect between binding agent and electrode active material, still can keep and combining closely between active material after active material produces larger volume change.Compare patent (application number: 200680029579.8) disclosed composite adhesive, composite adhesive of the present invention contains and can be conducive to the groups such as the carboxyl of lithium ion transport with electrode active material generation bonding, can to prevent from charge and discharge process, because of the shedding phenomenon that volumetric expansion causes, improving the cyclical stability of electrode materials.
Accompanying drawing explanation
Fig. 1 is lithium cell cycle performance test curve figure in the embodiment of the present invention 1;
Fig. 2 is lithium cell cycle performance test curve figure in embodiment 2;
Fig. 3 is lithium cell cycle performance test curve figure in embodiment 3;
Fig. 4 is lithium cell cycle performance test curve figure in comparative example 1;
Fig. 5 is lithium cell cycle performance test curve figure in comparative example 2.
Embodiment
Following embodiment is only described in further detail the present invention, but does not form any limitation of the invention.
Embodiment 1
Lithium ion battery enhancement type composite adhesive in the present embodiment, is made up of 0.01g carboxyl function carbon nano tube and 0.1g sodium alginate.
In the present embodiment, the preparation method of carboxyl function carbon nano tube comprises the following steps:
(1) prepare the mixed solution 120mL of the vitriol oil and concentrated nitric acid, the volume ratio of the vitriol oil and concentrated nitric acid is 3:1;
(2) in mixed solution, 3g carbon nanotube is added, under frequency 22kHz, power 500W condition ultrasonic 8 hours, at 120 DEG C, stirring and refluxing heats 2 hours again, supernatant liquor is removed after gained solution centrifugal, add deionized water concussion evenly rear recentrifuge, this is operated to supernatant liquor pH value and is greater than 6.5 repeatedly, and vacuum-drying at 120 DEG C, to obtain final product.
The preparation method of lithium ion battery enhancement type composite adhesive in the present embodiment, comprises the following steps:
(1) 0.1g sodium alginate is joined in 16mL deionized water, obtain even, transparent thick solution;
(2) the carboxyl function carbon nano tube of above-mentioned for 0.01g preparation is joined in the solution of step (1), ultrasonic to evenly, obtain composite adhered agent solution.
The application of enhancement type composite adhesive in lithium ion battery in the present embodiment, comprises the following steps:
(1) 0.3g nano silica fume, 0.1g superconduction carbon black are joined in the composite adhered agent solution of above-mentioned preparation, magnetic agitation ultrasonic disperse, obtain uniform mixed slurry;
(2) mixed slurry in step (1) is coated on Copper Foil, vacuum-drying 6 hours at 100 DEG C, the circular negative plate of radius 14mm, thickness 30 μm is made in punching again, at 100 DEG C, vacuum-drying is placed on and is full of in the glove box of argon gas, be to electrode with lithium sheet, 1M lithium hexafluoro phosphate (EC:DEC:DMC=1:1:1, V/V) is electrolytic solution, and celgard2400 barrier film is barrier film assembling half-cell.
Lithium ion half-cell discharge and recharge under 0.1C ~ 1C electric current in the present embodiment, reversible capacity reaches more than 2200mAh/g first, and remain on more than 2000mAh/g after 50 circulations, cycle efficiency is more than 90%, coulombic efficiency remains at more than 97%, and cycle performance test curve figure is shown in Fig. 1.
Embodiment 2
Lithium ion battery enhancement type composite adhesive in the present embodiment, is made up of 0.1g carboxyl function carbon nano tube and 0.1g cm-chitosan.
In the present embodiment, the preparation method of carboxyl function carbon nano tube comprises the following steps:
(1) prepare the mixed solution 120mL of the vitriol oil and concentrated nitric acid, the volume ratio of the vitriol oil and concentrated nitric acid is 3:2;
(2) in mixed solution, 3g carbon nanotube is added, under frequency 22kHz, power 500W condition ultrasonic 6 hours, at 60 DEG C, stirring and refluxing heats 12 hours again, supernatant liquor is removed after gained solution centrifugal, add deionized water concussion evenly rear recentrifuge, this is operated to supernatant liquor pH value and is greater than 6.5 repeatedly, and vacuum-drying at 120 DEG C, to obtain final product.
The preparation method of lithium ion battery enhancement type composite adhesive in the present embodiment, comprises the following steps:
(1) 0.1g cm-chitosan is joined in 8mL deionized water, obtain even, transparent thick solution;
(2) the carboxyl function carbon nano tube of above-mentioned for 0.1g preparation is joined in the solution of step (1), ultrasonic to evenly, obtain composite adhered agent solution.
The application of enhancement type composite adhesive in lithium ion battery in the present embodiment, comprises the following steps:
(1) 0.2g nano silica fume, 0.1g carbon nanotube are joined in the composite adhered agent solution of above-mentioned preparation, magnetic agitation ultrasonic disperse, obtain uniform mixed slurry;
(2) mixed slurry in step (1) is coated on Copper Foil, vacuum-drying 12 hours at 100 DEG C, the circular negative plate of radius 14mm, thickness 30 μm is made in punching again, at 100 DEG C, vacuum-drying is placed on and is full of in the glove box of argon gas, be to electrode with lithium sheet, 1M lithium hexafluoro phosphate (EC:DEC:DMC=1:1:1, V/V) is electrolytic solution, and celgard2400 barrier film is barrier film assembling half-cell.
Lithium ion half-cell discharge and recharge under 0.1C ~ 1C electric current in the present embodiment, reversible capacity reaches more than 2200mAh/g first, and remain on more than 1900mAh/g after 50 circulations, cycle efficiency is more than 86%, coulombic efficiency remains at more than 98%, and cycle performance test curve figure is shown in Fig. 2.
Embodiment 3
Lithium ion battery enhancement type composite adhesive in the present embodiment, is made up of 0.05g carboxyl function carbon nano tube and 0.1g Xylo-Mucine.
In the present embodiment, the preparation method of carboxyl function carbon nano tube comprises the following steps:
(1) prepare the mixed solution 120mL of the vitriol oil and concentrated nitric acid, the volume ratio of the vitriol oil and concentrated nitric acid is 2:1;
(2) in mixed solution, 2g carbon nanotube is added, under frequency 22kHz, power 500W condition ultrasonic 24 hours, at 80 DEG C, stirring and refluxing heats 10 hours again, supernatant liquor is removed after gained solution centrifugal, add deionized water concussion evenly rear recentrifuge, this is operated to supernatant liquor pH value and is greater than 6.5 repeatedly, and vacuum-drying at 120 DEG C, to obtain final product.
The preparation method of lithium ion battery enhancement type composite adhesive in the present embodiment, comprises the following steps:
(1) 0.1g Xylo-Mucine is joined in 6mL deionized water, obtain even, transparent thick solution;
(2) the carboxyl function carbon nano tube of above-mentioned for 0.05g preparation is joined in the solution of step (1), ultrasonic to evenly, obtain composite adhered agent solution.
The application of enhancement type composite adhesive in lithium ion battery in the present embodiment, comprises the following steps:
(1) 0.2g nano silica fume, 0.1g carbon fiber are joined in the composite adhered agent solution of above-mentioned preparation, magnetic agitation ultrasonic disperse, obtain uniform mixed slurry;
(2) mixed slurry in step (1) is coated on Copper Foil, vacuum-drying 6 hours at 100 DEG C, the circular negative plate of radius 14mm, thickness 30 μm is made in punching again, at 100 DEG C, vacuum-drying is placed on and is full of in the glove box of argon gas, be to electrode with lithium sheet, 1M lithium hexafluoro phosphate (EC:DEC:DMC=1:1:1, V/V) is electrolytic solution, and celgard2400 barrier film is barrier film assembling half-cell.
Lithium ion half-cell discharge and recharge under 0.1C ~ 1C electric current in the present embodiment, reversible capacity reaches more than 2000mAh/g first, and remain on more than 1700mAh/g after 50 circulations, cycle efficiency is more than 85%, coulombic efficiency remains at more than 97%, and cycle performance test curve figure is shown in Fig. 3.
Embodiment 4
Lithium ion battery enhancement type composite adhesive in the present embodiment, is made up of 0.05g carboxyl function carbon nano tube and 0.1g sodium starch glycolate.
In the present embodiment, the preparation method of carboxyl function carbon nano tube comprises the following steps:
(1) prepare the mixed solution 120mL of the vitriol oil and concentrated nitric acid, the volume ratio of the vitriol oil and concentrated nitric acid is 3:2
(2) in mixed solution, 2g carbon nanotube is added, under frequency 22kHz, power 500W condition ultrasonic 6 hours, at 60 DEG C, stirring and refluxing heats 12 hours again, supernatant liquor is removed after gained solution centrifugal, add deionized water concussion evenly rear recentrifuge, this is operated to supernatant liquor pH value and is greater than 6.5 repeatedly, and vacuum-drying at 120 DEG C, to obtain final product.
The preparation method of lithium ion battery enhancement type composite adhesive in the present embodiment, comprises the following steps:
(1) 0.1g sodium starch glycolate is joined in 6mL deionized water, obtain even, transparent thick solution;
(2) the carboxyl function carbon nano tube of above-mentioned for 0.05g preparation is joined in the solution of step (1), ultrasonic to evenly, obtain composite adhered agent solution.
The application of enhancement type composite adhesive in lithium ion battery in the present embodiment, comprises the following steps:
(1) 0.3g nano silica fume, 0.15g carbon fiber are joined in the composite adhered agent solution of above-mentioned preparation, magnetic agitation ultrasonic disperse, obtain uniform mixed slurry;
(2) mixed slurry in step (1) is coated on Copper Foil, vacuum-drying 6 hours at 100 DEG C, the circular negative plate of radius 14mm, thickness 30 μm is made in punching again, at 100 DEG C, vacuum-drying is placed on and is full of in the glove box of argon gas, be to electrode with lithium sheet, 1M lithium hexafluoro phosphate (EC:DEC:DMC=1:1:1, V/V) is electrolytic solution, and celgard2400 barrier film is barrier film assembling half-cell.
Lithium ion half-cell discharge and recharge under 0.1C ~ 1C electric current in the present embodiment, reversible capacity reaches more than 2100mAh/g first, and remain on more than 1700mAh/g after 50 circulations, cycle efficiency is more than 80%, and coulombic efficiency remains at more than 96%.
Embodiment 5
Lithium ion battery enhancement type composite adhesive in the present embodiment, is made up of 0.01g carboxyl function carbon nano tube and 0.1g carboxymethyl chitin.
In the present embodiment, the preparation method of carboxyl function carbon nano tube comprises the following steps:
(1) prepare the mixed solution 120mL of the vitriol oil and concentrated nitric acid, the volume ratio of the vitriol oil and concentrated nitric acid is 3:2
(2) in mixed solution, 4g carbon nanotube is added, under frequency 22kHz, power 500W condition ultrasonic 6 hours, after at 60 DEG C stirring and refluxing heat 12 hours, supernatant liquor is removed after gained solution centrifugal, add deionized water concussion evenly rear recentrifuge, this is operated to supernatant liquor pH value and is greater than 6.5 repeatedly, and vacuum-drying at 120 DEG C, to obtain final product.
The preparation method of lithium ion battery enhancement type composite adhesive in the present embodiment, comprises the following steps:
(1) 0.1g carboxymethyl chitin is joined in 6mL deionized water, obtain even, transparent thick solution;
(2) the carboxyl function carbon nano tube of above-mentioned for 0.01g preparation is joined in the solution of step (1), ultrasonic to evenly, obtain composite adhered agent solution.
The application of enhancement type composite adhesive in lithium ion battery in the present embodiment, comprises the following steps:
(1) 0.5g nano silica fume, 0.05g nickel fiber are joined in the composite adhered agent solution of above-mentioned preparation, magnetic agitation ultrasonic disperse, obtain uniform mixed slurry;
(2) mixed slurry in step (1) is coated on Copper Foil, vacuum-drying 6 hours at 100 DEG C, the circular negative plate of radius 14mm, thickness 30 μm is made in punching again, at 100 DEG C, vacuum-drying is placed on and is full of in the glove box of argon gas, be to electrode with lithium sheet, 1M lithium hexafluoro phosphate (EC:DEC:DMC=1:1:1, V/V) is electrolytic solution, and celgard2400 barrier film is barrier film assembling half-cell.
Lithium ion half-cell discharge and recharge under 0.1C ~ 1C electric current in the present embodiment, reversible specific capacity reaches more than 1900mAh/g first, and remain on more than 1500mAh/g after 50 circulations, cycle efficiency is more than 78%, and coulombic efficiency remains at more than 96%.
Embodiment 6
Lithium ion battery enhancement type composite adhesive in the present embodiment, is made up of 0.05g carboxyl function carbon nano tube and 0.1g croscarmellose sodium.
In the present embodiment in the preparation method of lithium ion battery enhancement type composite adhesive and application, except vacuum-drying 1 hour at latter 150 DEG C of coating, other are all identical with embodiment 3.
Lithium ion half-cell discharge and recharge under 0.1C ~ 1C electric current in the present embodiment, reversible capacity reaches more than 2300mAh/g first, and remain on more than 2100mAh/g after 50 circulations, cycle efficiency is more than 91%, and coulombic efficiency remains at more than 98%.
Embodiment 7
Lithium ion battery enhancement type composite adhesive in the present embodiment, is made up of 0.01g carboxyl function carbon nano tube and 0.1g Xylo-Mucine-sodium starch glycolate cross-linking products.
In the present embodiment, the preparation method of carboxyl function carbon nano tube comprises the following steps:
(1) prepare the mixed solution 120mL of the vitriol oil and concentrated nitric acid, the volume ratio of the vitriol oil and concentrated nitric acid is 3:1;
(2) in mixed solution, 3g carbon nanotube is added, under frequency 22kHz, power 500W condition ultrasonic 8 hours, at 120 DEG C, stirring and refluxing heats 2 hours again, supernatant liquor is removed after gained solution centrifugal, add deionized water concussion evenly rear recentrifuge, this is operated to supernatant liquor pH value and is greater than 6.5 repeatedly, and vacuum-drying at 120 DEG C, to obtain final product.
The preparation method of lithium ion battery enhancement type composite adhesive in the present embodiment, comprises the following steps:
(1) 0.05g Xylo-Mucine and 0.05g sodium starch glycolate are joined in 16mL deionized water, obtain even, transparent thick solution;
(2) the carboxyl function carbon nano tube of above-mentioned for 0.01g preparation is joined in the solution of step (1), ultrasonic to evenly, obtain composite adhered agent solution.
The application of enhancement type composite adhesive in lithium ion battery in the present embodiment, comprises the following steps:
(1) 0.3g nano silica fume, 0.1g superconduction carbon black, linking agent (polyacrylic acid), initiator (Potassium Persulphate) are joined in the composite adhered agent solution of above-mentioned preparation, magnetic agitation ultrasonic disperse, obtain uniform mixed slurry;
(2) mixed slurry in step (1) is coated on Copper Foil, vacuum-drying 2 hours at 120 DEG C, the circular negative plate of radius 14mm, thickness 30 μm is made in punching again, at 100 DEG C, vacuum-drying is placed on and is full of in the glove box of argon gas, be to electrode with lithium sheet, 1M lithium hexafluoro phosphate (EC:DEC:DMC=1:1:1, V/V) is electrolytic solution, and celgard2400 barrier film is barrier film assembling half-cell.
Lithium ion half-cell discharge and recharge under 0.1C ~ 1C electric current in the present embodiment, reversible capacity reaches more than 2300mAh/g first, and remain on more than 2000mAh/g after 50 circulations, cycle efficiency is more than 86%, and coulombic efficiency remains at more than 97%.
Comparative example 1
Lithium ion battery composite adhesive in this comparative example, is made up of 0.05g carbon nanotube and 0.1g sodium alginate.
The preparation method of lithium ion battery composite adhesive in this comparative example, comprises the following steps:
(1) 0.1g sodium alginate is joined in 6mL deionized water, obtain even, transparent thick solution;
(2) 0.05g carbon nanotube is joined in the solution of step (1), ultrasonic to evenly, obtain composite adhered agent solution.
The application of composite adhesive in lithium ion battery in this comparative example, comprises the following steps:
(1) 0.3g nano silica fume, 0.1g superconduction carbon black are joined in the composite adhered agent solution of above-mentioned preparation, magnetic agitation ultrasonic disperse, obtain uniform mixed slurry;
(2) mixed slurry in step (1) is coated on Copper Foil, vacuum-drying 6 hours at 150 DEG C, the circular negative plate of radius 14mm, thickness 30 μm is made in punching again, at 120 DEG C, vacuum-drying is placed on and is full of in the glove box of argon gas, with lithium sheet be to electrode, 1M lithium hexafluoro phosphate (EC:DEC:DMC=1:1:1, V/V) be electrolytic solution, celgard2400 barrier film is barrier film assembling half-cell.
Lithium ion half-cell discharge and recharge under 0.1C ~ 1C electric current in this comparative example, reversible capacity reaches more than 2200mAh/g first, more than 1500mAh/g is remained on after 50 circulations, cycle efficiency is more than 68%, be reduced to about 95% at coulombic efficiency after high rate charge-discharge, cycle performance test curve figure is shown in Fig. 4.
Comparative example 2
Lithium ion battery composite adhesive in this comparative example, is made up of 0.05g carboxyl function carbon nano tube and 0.1g PVDF.
In this comparative example, the preparation method of carboxyl function carbon nano tube comprises the following steps:
(1) prepare the mixed solution 120mL of the vitriol oil and concentrated nitric acid, the volume ratio of the vitriol oil and concentrated nitric acid is 3:1;
(2) in mixed solution, 3g carbon nanotube is added, under frequency 22kHz, power 500W condition ultrasonic 8 hours, at 120 DEG C, stirring and refluxing heats 2 hours again, supernatant liquor is removed after gained solution centrifugal, add deionized water concussion evenly rear recentrifuge, this is operated to supernatant liquor pH value and is greater than 6.5 repeatedly, and vacuum-drying at 120 DEG C, to obtain final product.
The preparation method of lithium ion battery composite adhesive in this comparative example, comprises the following steps:
(1) 0.1g PVDF is joined in 8mL NMP, obtain even, transparent solution;
(2) the carboxyl function carbon nano tube of above-mentioned for 0.05g preparation is joined in the solution of step (1), ultrasonic to evenly, obtain composite adhered agent solution.
The application of composite adhesive in lithium ion battery in this comparative example, comprises the following steps:
(1) join in the composite adhered agent solution of above-mentioned preparation by 0.2g nano silica fume, 0.2g carbon nanotube, ball milling (12 hours), obtains uniform mixed slurry;
(2) mixed slurry in step (1) is coated on Copper Foil, vacuum-drying 12 hours at 100 DEG C, the circular negative plate of radius 14mm, thickness 30 μm is made in punching again, at 100 DEG C, vacuum-drying is placed on and is full of in the glove box of argon gas, with lithium sheet be to electrode, 1M lithium hexafluoro phosphate (EC:DEC:DMC=1:1:1, V/V) be electrolytic solution, celgard2400 barrier film is barrier film assembling half-cell.
Lithium ion half-cell discharge and recharge under 0.1C ~ 1C electric current in the present embodiment, reversible capacity reaches more than 2200mAh/g first, and remain on more than 350mAh/g after 50 circulations, cycle efficiency is low to moderate 16%, and cycle performance test curve figure is shown in Fig. 5.
Claims (10)
1. a lithium ion battery enhancement type composite adhesive, it is characterized in that: be made up of carboxyl function carbon nano tube and the water-soluble polymer containing A, B two kinds of groups, A group is carboxyl, and B group is hydroxyl and/or amino, and the mass ratio of described carbon nanotube and water-soluble polymer is 0.1 ~ 1.
2. lithium ion battery enhancement type composite adhesive according to claim 1, it is characterized in that: the preparation method of described carboxyl function carbon nano tube is: carbon nanotube is added in the mixed solution of the vitriol oil and concentrated nitric acid, reflux 2 ~ 12 hours at 60 ~ 120 DEG C after ultrasonic, washing, drying.
3. lithium ion battery enhancement type composite adhesive according to claim 2, is characterized in that: in described mixed solution, the volume ratio of the vitriol oil and concentrated nitric acid is 3:(1 ~ 2).
4. lithium ion battery enhancement type composite adhesive according to claim 1, it is characterized in that: described water-soluble polymer is any one in sodium alginate, Xylo-Mucine, cm-chitosan, carboxymethyl chitin, sodium starch glycolate, or the above-mentioned cross-linked hydrogel that several are formed.
5. a preparation method for the lithium ion battery enhancement type composite adhesive according to any one of Claims 1 to 4, is characterized in that: comprise the following steps: carboxyl function carbon nano tube and water-soluble polymer are added to the water, mix.
6. the application of lithium ion battery enhancement type composite adhesive in lithium cell according to any one of Claims 1 to 4.
7. the application of enhancement type composite adhesive according to claim 6 in lithium cell, is characterized in that: the consumption of composite adhesive is 20 ~ 50% of negative active core-shell material quality.
8. the application of enhancement type composite adhesive according to claim 6 in lithium cell, is characterized in that: described negative active core-shell material is carbon class, silicon class, tin class and matrix material thereof.
9. the application of enhancement type composite adhesive according to claim 8 in lithium cell, is characterized in that: described negative active core-shell material is one or more in natural graphite, electrographite, MCMB, biomass charcoal, nano-silicon, silicon-carbon mixture, silicon alloy, Si oxide, tin-based oxide, tin-based alloy, tin carbon complex.
10. the application of enhancement type composite adhesive according to claim 6 in lithium cell, is characterized in that: containing conductive agent in the electrode materials of described lithium cell, the consumption of conductive agent is 10 ~ 50% of negative active core-shell material quality.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105489898A (en) * | 2015-12-31 | 2016-04-13 | 深圳市贝特瑞新能源材料股份有限公司 | Conductive waterborne binder and preparation method therefor, and lithium ion battery |
| CN105702963A (en) * | 2016-01-29 | 2016-06-22 | 长沙理工大学 | Application of carboxymethyl chitosan self-crosslinking polymer in silicon negative electrode of lithium ion battery |
| CN105762364A (en) * | 2016-04-25 | 2016-07-13 | 深圳大学 | Battery negative electrode, preparing method of battery negative electrode and lithium ion battery |
| CN108695508A (en) * | 2018-07-06 | 2018-10-23 | 辽宁九夷锂能股份有限公司 | High-energy lithium battery negative electrode slurry and preparation method thereof |
| CN109134757A (en) * | 2018-07-16 | 2019-01-04 | 合肥国轩高科动力能源有限公司 | A kind of modification of chitosan and preparation method thereof and purposes |
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| CN109755579A (en) * | 2018-12-29 | 2019-05-14 | 山东华夏神舟新材料有限公司 | The preparation method of the positive composite conducting binder of lithium ion battery |
| CN110546788A (en) * | 2017-02-24 | 2019-12-06 | 纳米技术仪器公司 | Polymer binder for lithium battery and manufacturing method |
| CN110582872A (en) * | 2017-02-27 | 2019-12-17 | 纳米技术仪器公司 | Lithium battery cathode and method of manufacture |
| CN111293312A (en) * | 2020-02-21 | 2020-06-16 | 上海交通大学 | Flexible multifunctional cross-linking adhesive and preparation method and application thereof |
| WO2021195913A1 (en) * | 2020-03-31 | 2021-10-07 | 宁德新能源科技有限公司 | Negative electrode material, negative electrode sheet, electrochemical device, and electronic device |
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| CN115703751A (en) * | 2021-08-16 | 2023-02-17 | 广西至善新材料科技有限公司 | Preparation method of gallic acid glycidyl ester and adhesive thereof |
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| CN105489898B (en) * | 2015-12-31 | 2019-02-05 | 深圳市贝特瑞新能源材料股份有限公司 | Conductive aqueous binders and preparation method thereof, lithium ion battery |
| CN105489898A (en) * | 2015-12-31 | 2016-04-13 | 深圳市贝特瑞新能源材料股份有限公司 | Conductive waterborne binder and preparation method therefor, and lithium ion battery |
| CN105702963A (en) * | 2016-01-29 | 2016-06-22 | 长沙理工大学 | Application of carboxymethyl chitosan self-crosslinking polymer in silicon negative electrode of lithium ion battery |
| CN105702963B (en) * | 2016-01-29 | 2018-06-29 | 长沙理工大学 | A kind of application of carboxymethyl chitosan self-crosslinking polymer in lithium ion battery silicium cathode |
| CN105762364A (en) * | 2016-04-25 | 2016-07-13 | 深圳大学 | Battery negative electrode, preparing method of battery negative electrode and lithium ion battery |
| CN105762364B (en) * | 2016-04-25 | 2019-01-25 | 深圳大学 | Battery negative electrodes and preparation method thereof and lithium ion battery |
| CN110546788A (en) * | 2017-02-24 | 2019-12-06 | 纳米技术仪器公司 | Polymer binder for lithium battery and manufacturing method |
| CN110546788B (en) * | 2017-02-24 | 2023-05-12 | 纳米技术仪器公司 | Polymer binder for lithium battery and method of manufacturing the same |
| CN110582872B (en) * | 2017-02-27 | 2023-05-12 | 纳米技术仪器公司 | Lithium battery cathode and method of manufacture |
| CN110582872A (en) * | 2017-02-27 | 2019-12-17 | 纳米技术仪器公司 | Lithium battery cathode and method of manufacture |
| CN108695508A (en) * | 2018-07-06 | 2018-10-23 | 辽宁九夷锂能股份有限公司 | High-energy lithium battery negative electrode slurry and preparation method thereof |
| CN108695508B (en) * | 2018-07-06 | 2022-05-13 | 辽宁九夷锂能股份有限公司 | High-energy lithium battery negative electrode slurry and preparation method thereof |
| CN109134757B (en) * | 2018-07-16 | 2020-12-11 | 合肥国轩高科动力能源有限公司 | Modified chitosan, preparation method and application thereof |
| CN109134757A (en) * | 2018-07-16 | 2019-01-04 | 合肥国轩高科动力能源有限公司 | A kind of modification of chitosan and preparation method thereof and purposes |
| CN109411758A (en) * | 2018-10-19 | 2019-03-01 | 深圳市优宝新材料科技有限公司 | A kind of preparation method of negative electrode of lithium ion battery water system electroconductive binder |
| CN109411758B (en) * | 2018-10-19 | 2020-09-29 | 深圳市优宝新材料科技有限公司 | Preparation method of aqueous conductive adhesive for lithium ion battery cathode |
| CN109755579A (en) * | 2018-12-29 | 2019-05-14 | 山东华夏神舟新材料有限公司 | The preparation method of the positive composite conducting binder of lithium ion battery |
| CN109755579B (en) * | 2018-12-29 | 2020-12-01 | 山东华夏神舟新材料有限公司 | Preparation method of positive electrode composite conductive adhesive for lithium ion battery |
| CN111293312A (en) * | 2020-02-21 | 2020-06-16 | 上海交通大学 | Flexible multifunctional cross-linking adhesive and preparation method and application thereof |
| CN111293312B (en) * | 2020-02-21 | 2024-02-20 | 上海交通大学 | Flexible multifunctional crosslinking adhesive and preparation method and application thereof |
| CN113728471A (en) * | 2020-03-31 | 2021-11-30 | 宁德新能源科技有限公司 | Negative electrode material, negative electrode sheet, electrochemical device, and electronic device |
| WO2021195913A1 (en) * | 2020-03-31 | 2021-10-07 | 宁德新能源科技有限公司 | Negative electrode material, negative electrode sheet, electrochemical device, and electronic device |
| CN113728471B (en) * | 2020-03-31 | 2023-09-05 | 宁德新能源科技有限公司 | Negative electrode material, negative electrode sheet, electrochemical device, and electronic device |
| CN115703751A (en) * | 2021-08-16 | 2023-02-17 | 广西至善新材料科技有限公司 | Preparation method of gallic acid glycidyl ester and adhesive thereof |
| CN115703751B (en) * | 2021-08-16 | 2024-05-07 | 广西至善新材料科技有限公司 | Preparation method of glycidyl gallate and adhesive thereof |
| CN114361426A (en) * | 2022-01-25 | 2022-04-15 | 山西大学 | Preparation method and application of biomass-based silicon-carbon composite material |
| CN115799610A (en) * | 2023-02-06 | 2023-03-14 | 星源材质(南通)新材料科技有限公司 | Composite membrane and preparation method thereof, PVDF microporous membrane wrapping lithium salt grafted carbon nanotube and solid-state battery |
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