CN105702963B - A kind of application of carboxymethyl chitosan self-crosslinking polymer in lithium ion battery silicium cathode - Google Patents
A kind of application of carboxymethyl chitosan self-crosslinking polymer in lithium ion battery silicium cathode Download PDFInfo
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Abstract
The invention discloses a kind of application of carboxymethyl chitosan self-crosslinking polymer in lithium ion battery；Carboxymethyl chitosan self-crosslinking polymer adds in crosslinking agent 1 (3 dimethylamino-propyl) 3 ethyl carbon Asia diamines by carboxymethyl chitosan and is obtained by self-crosslinking, it is with 3-D solid structure, it is applied to prepare lithium ion battery silicium cathode as binding agent, show good mechanical performance, adhesive property and chemical bond of the formation with self-reparing capability between silicon particle, caused large volume variation of the silicium cathode in charge and discharge process can effectively be accommodated, solve silicium cathode in cyclic process due to the violent volume change of silicon particle and caused by structural damage shedding phenomenon, cycle performance to improve lithium ion battery silicium cathode provides a kind of new approach.
Description
Technical field
The present invention relates to a kind of carboxymethyl chitosan self-crosslinking polymers to be used as silicium cathode binding agent in lithium ion battery
Application, and in particular to a kind of modification biological natural polymer binding agent preparation and its application in lithium battery silicium cathode,
It is related to technical field of lithium batteries.
Background technology
With the development of mancarried electronic aid and electric vehicle, requirement of the people to the energy density of lithium battery is also increasingly
It improves.In order to improve the energy density of lithium battery, the performance of each component part (anode, cathode, electrolyte and diaphragm) is all
It is to be improved.In terms of negative material, traditional negative material graphite is due to its relatively low theoretical capacity (372mAhg-1) not
The requirement of high-energy density can be met, researcher is to the research pay attention to day by day of height ratio capacity negative material.IV races elemental silicon due to
It has the theoretical capacity (4200mAhg of superelevation-1) as the hot spot of next-generation lithium ion battery negative material area research.But
Nano-silicon as the defects of negative material be battery in charge and discharge process due to the deintercalation of a large amount of lithium ions cause it is violent
Volume expansion (300%), the volume change in cyclic process repeatedly will be disconnected gradually between silicon and other components, made
Nano-silicon and conductive agent lose electronic contact, and come off from collector, and battery capacity is caused to decay.
In order to improve the performance of silicium cathode and its cycle life, researchers, which report, prepares silicon substrate multiple elements design material
The methods of material, the diameter of control silicon particle, improvement slurry spraying technology, design prepare high-performance adhesive.Wherein, enhance electrode
Between the interaction of each component be to solve silicium cathode material rapid effective approach of capacity attenuation in cyclic process.Selection
Suitable high-performance adhesive is then to increase one of effective way of interaction of each component in electrode.Common binding agent gathers partially
Vinyl fluoride (PVDF) when for silicium cathode since PVDF is easily plastically deformed, when silicium cathode volume change is larger, nanometer
Silicon and conductive agent, which are easily filled on pole piece, to come off.And since its dispersant N-Methyl pyrrolidone (NMP) is expensive and toxic
The shortcomings of, the research of novel binders is particularly important.At present.Silicium cathode binding agent presently, there are main problem be：
(1) adhesive property is not strong, it is impossible to strong interaction is generated between active material and other components；(2) cost of material is held high
Expensive, preparation process is complicated, is not suitable for mass producing；(3) environmental pollution is also easy to produce in preparation process, does not meet green production
Requirement.
Biomaterial derives from a wealth of sources as a kind of renewable resource, has been used for every field.2011, Kovalenko
Etc. reporting application (Science, 334 (2011) 75) of the sodium alginate in silicium cathode.When silicium cathode use is carried from brown alga
When the water soluble polymer sodium alginate taken is as binding agent, in 4200mAg-1Reversible capacity after being recycled 100 times under electric current is big
In 1700mAhg-1, and use PVDF as the silicium cathode reversible capacity under the same conditions of binding agent already close to zero.Liu
Deng using boiomacromolecule guar gum GG) as binding agent for (Advanced Functional in silicium cathode
Materials,25(2015)3599).Research shows that the GG with a large amount of polar functional group can be formed more with silicon atom surface
Strong interaction, while GG can improve the electric conductivity of pole piece.
The polymer of hydroxyl and carboxyl is that most commonly used a kind of binding agent is studied in silicium cathode.Hydroxy functional group has
Hydrophily, therefore the polymeric binder of hydroxyl is generally dissolved in water, this kind of binding agent can use water to be used for as dispersant
Pole piece production so as to avoid use organic solvent as dispersant and caused by environmental pollution.Carboxyl functional group energy and titanium dioxide
Generation is with the hydrogen bond to interact strongly between silicon (being present in silicon atom surface) and copper (or oxide of copper).Also,
It is reported that the hydrogen bond generated between them have self-reparing capability, be destroyed after can be spontaneous carry out self-regeneration.Cause
This, relative to the polymeric binder (such as PVDF, styrene-dibutene rubber (SBR)) without carboxyl functional group, contains hydroxyl
Or polymeric binder and its derivative (such as sodium alginate, polyacrylic acid (PAA), the carboxymethyl cellulose of carboxyl functional group
(CMC), carboxymethyl chitosan etc.) for silicium cathode show better chemical property.
Chitosan is the modified product of the chitin in shrimp shell, contains abundant hydroxyl.Zheng etc., which is reported, gathers shell
Sugar is as binding agent for graphite cathode (Electrochimica Acta, 105 (2013) 378), relatively existing binding agent material
Material can improve the cycle performance of pole piece to a certain extent.In addition, carboxymethyl chitosan is used as silicium cathode binding agent by Yue etc.
Relatively existing binding agent also illustrates good performance (Journal Of Power Sources, 247 (2014) 327)；Though
Right carboxymethyl chitosan can be formed with silicon face with certain self-healing properties using a large amount of carboxyls and hydroxyl that it contains
Hydrogen bond improves the cycle performance of silicium cathode；But it is limited by the self-repairing capability of hydrogen bond, it can not thoroughly solve charge and discharge
Since the deintercalation of a large amount of lithium ions leads to violent volume expansion in electric process, and the volume in cyclic process repeatedly is caused to become
Change, will gradually be disconnected between silicon and other components, nano-silicon and conductive agent is made to lose electronic contact, and taken off from collector
The defects of falling, battery capacity caused to decay.
Current research finds that compared with chain high molecular polymer binder, the polymeric binder of three-dimensional structure has
Better mechanical property and three-dimensional overall structure protective capability, are expected to improve the cycle performance of cathode and effective specific capacity.Jeong
Etc. report using hyperbranched beta cyclo dextrin polymer (β-CDp) as lithium ion battery Si negative electrode binders (Nano Letters,
14(2014)864).It is found by peel test, each component using β-CDp as the pole piece of binding agent is relative to using seaweed
Sour sodium is closer as binding agent, and bond effect is more preferable.They point out, relative to the linear structure of sodium alginate, the three of β-CDp
Dimension reticular structure can effectively inhibit volume change of the Si particles in charge and discharge process.In 1C (4200mAg-1) current density
After lower cycle 150 times, the capacity retention ratio of pole piece using β-CDp and the pole piece using sodium alginate be respectively 50.6% with
27.1%, and the Si cathode using PVDF as binding agent have just failed after 10 cycles.
Cross linked polyacrylate (PAA) and the polyvinyl alcohol (PVA) by way of being cross-linked in situ such as Song obtain a kind of new
Gelatin polymer binding agent.The reticular structure of this gel polymer electrolyte can effectively buffer lithium battery in high current charge-discharge
When silicon particle volume change violent caused by the deintercalation of lithium ion, use PAA-PVA polymer gel binding agents
Capacity per unit area can reach 4.3mAh/cm2(Advanced Functional Materials.24(2014)5904-
5910).Gel effect can effectively improve the rheological property of slurry.The friendship of gelatin polymer binding agent obtained using this method
Connection degree fails to obtain quantitative control, therefore the performance of silicium cathode made from this binding agent and unstable.
Koo etc. obtains a kind of three-dimensional polymer binding agent using PAA and CMC by polycondensation reaction.Use the binding agent
Silicium cathode is in 175mAg-1Reversible capacity after being recycled 100 times under current density reaches 2000mAhg-1, in 30Ag-1Electric current it is close
It spends, the reversible capacity at a temperature of 60 DEG C is up to 1500mAhg-1。(Angewandte Chemie-International
Edition.51(2012)8762-8767).Liu et al. is reported the styrene butadiene ribber (SBR) and Na-CMC of elastomer
It is mixed and modified to be used as Si negative electrode binders (Electrochemical And Solid State Letters, 8 (2005)
A100).This hybrid adhesive can improve the swelling behavior of the mechanical property and pole piece of pole piece in the electrolytic solution.But by
Compatibility between SBR and Na-CMC is not fine, and the performance of this hybrid adhesive need to be improved.
Japan Patent (JP2003282061) and (JP2006215761) etc. propose using nitrile rubber or butadiene with
The mode of fluoro containing polymers mechanical blending generates a kind of high-performance adhesive.Although the flexibility and caking property of binding agent have compared with
Big raising, but since it uses physical mechanical to be blended so binding agent internal mix obtains not uniform enough, is configured
Slurry will appear lamination after the standing.Due to not interacting between two kinds of polymer, pole piece is in use
Segregation phenomenon can be generated, influences the cycle performance of pole piece.
China Dongfang Electric Group Corporation discloses a kind of preparation method of compound water-soluble binder
(CN201110427929).This method utilizes amorphous poly ethylene oxide Type of Collective object aqueous solution and gel-type water-soluble binder
It carries out block polymerization and obtains.The binding agent has preferable compliance, improves the flexibility of pole piece, while combine two kinds
The advantages of water soluble polymer, improves the capacity and cycle performance of pole piece.But the preparation process of the binding agent is more complicated, and
The pole piece performance boost being worth is not obvious.Hubei Wanrun New Energy Technology Development Co., Ltd. discloses a kind of compoiste adhering
The preparation method and application (CN201310364057) of agent.A kind of macromolecule containing carboxyl functional group is contained hydroxyl by this method with a kind of
The macromolecule of base functional group is formed by adding in crosslinking agent heat cross-linking, and obtained binding agent has good plasticity
And adhesive property.The invention must take into consideration the compatibility and ratio problems of two kinds of polymer in the preparation.
Invention content
For polymeric binder in the prior art, there are adhesive property is poor, preparation process complexity, self-repair function difference etc.
Problem, and existing lithium battery silicium cathode material application requirement can not be met, the purpose of the invention is to provide one kind to have
The application of the carboxymethyl chitosan self-crosslinking polymer of 3-D solid structure, the cross-linked polymer show good mechanicalness
Can, adhesive property and chemical bond self-reparing capability, can effectively solve silicium cathode in cyclic process silicon particle due to violent
Volume change and caused by structural damage.
In order to realize above-mentioned technical purpose, the present invention provides a kind of application of carboxymethyl chitosan self-crosslinking polymer,
It is applied to prepare lithium ion battery silicium cathode using carboxymethyl chitosan self-crosslinking polymer as binding agent；
The carboxymethyl chitosan self-crosslinking polymer is by carboxymethyl chitosan and 1- (3- dimethylamino-propyls) -3- second
Base carbodiimide (EDC) is obtained by cross-linking reaction.
Preferred scheme, carboxymethyl chitosan self-crosslinking polymer are prepared via a method which to obtain：In carboxymethyl chitosan
EDC and n-hydroxysuccinimide are added in sugar juice, the pH value for controlling solution is 5~7, is handed at a temperature of 20~40 DEG C
Connection reaction to get.
Preferred scheme, the addition of EDC are the 10~30% of carboxymethyl chitosan mole；More preferably for 10~
20%.
Preferred scheme, cross-linking reaction time are 20~25h.
Preferred scheme, carboxymethyl chitosan self-crosslinking polymer molecular weight are more than 3.5kDa.
Preferred scheme, lithium ion battery silicium cathode are prepared by the raw material including following mass percent component
It arrives：Silicon materials 70~90%, conductive agent 5~15%, the binding agent 5~15%.
Preferred scheme, the quality of binding agent are the 10~15% of silicon materials quality.
Preferred scheme, silicon materials are nano-silicon.
Preferred scheme, conductive agent are at least one of carbon nanotube, superconduction carbon black, graphite, high electric conductivity carbon, graphene.
More preferably scheme, cross-linking reaction time are 20~25h.
More preferably scheme, mixed solution carries out dialysis treatment, the retention of ultrafiltration membrane by ultrafiltration membrane obtained by cross-linking reaction
Molecular weight is 3.5kDa.
The carboxymethyl chitosan self-crosslinking polymer of the present invention is prepared by following steps：
(1) carboxymethyl chitosan is dissolved in the carboxymethyl chitosan solution that 1~2wt% is configured in deionized water；
(2) 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides and n-hydroxysuccinimide are sequentially added into carboxylic first
After in base chitosan solution, it is 5~7 to adjust pH value, is reacted 20~30 hours under room temperature environment；
(3) reaction product of above-mentioned gained is placed in dialysis purification 1~3 day in deionized water, removal molecular weight is less than
The molecular weight polymers and small molecule by-product of 3.5kDa, obtain binding agent hydrogel.
The n-hydroxysuccinimide used in the solution of the present invention is used for improving cross-linking efficiency.
Compared with prior art, beneficial effects of the present invention are：
(1) for technical scheme of the present invention by carrying out self-crosslinking modification to carboxymethyl chitosan, what is obtained has multidimensional net
The carboxymethyl chitosan self-crosslinking polymer of shape structure, it is low with preferable mechanical performance, crystallinity, and be crosslinked by EDC
It introduces partial amides key and itself contains the active force between great amount of hydroxy group, carboxyl and amino, with silicon materials and collector
By force, good cementation can be played.
(2) carboxymethyl chitosan self-crosslinking polymer of the invention makes full use of its multidimensional network structure, can effectively hold
Receive silicium cathode in charge and discharge process caused large volume variation, solve silicium cathode in cyclic process silicon particle due to violent
Volume change and caused by structural damage.
(3) carboxymethyl chitosan self-crosslinking polymer of the invention remains suitable carboxyl and hydroxyl and amino, water-soluble
Property it is preferable, can be generated with silicon face can selfreparing chemical bond, effectively improve the cycle performance of pole piece.
(4) requirement of preparation process composite green safety in production, easy to operate, easily controllable, feasibility is high, is suitble to industry
Change large-scale production.
Description of the drawings
【Fig. 1】For embodiment 1 and the infrared spectrum of the carboxymethyl chitosan of the different self-crosslinking degree of comparative example 1~3
Figure；
【Fig. 2】For embodiment 1 and the solution thereon of the carboxymethyl chitosan of the different self-crosslinking degree of comparative example 1~3；
【Fig. 3】It is embodiment 1 and the different carboxymethyl chitosan self-crosslinking polymers of comparative example 1~3 as binding agent
The cycle performance comparison diagram of silicium cathode obtained；
【Fig. 4】To use the cyclicity of silicium cathode made from carboxymethyl chitosan self-crosslinking polymer in comparative example 4
It can figure.
Specific embodiment
With reference to embodiment, the present invention is described further, but the claims in the present invention protection domain is not formed
Any restrictions are only used for helping to understand the content of present invention.
Embodiment 1
1st, the preparation of carboxymethyl chitosan self-crosslinking polymer：
1) 164mg carboxymethyl chitosans (C-chitosan) are dissolved in the C-chitosan that 1wt% is configured in deionized water
Solution.
2) above-mentioned acquired solution is sequentially added into 0.5mL0.5mol.L-1(molal quantity is about carboxymethyl chitosan to EDC
And 1mol.L 17%)-1NHS solution reacts 24 hours at room temperature；Solution is controlled by adding in appropriate NaOH and HCl solution
PH value is 5.5 or so.
3) reaction product mixture obtained by step 2) is subjected to dialysis purification, MWCO=3.5kDa is set to remove in reaction
The small molecule of generation, obtain carboxymethyl chitosan self-crosslinking polymer hydrogel to get.
The dissolubility of the carboxymethyl chitosan self-crosslinking polymer of preparation is as shown in compound C-C-C-1 in Fig. 2, from Fig. 2
In as can be seen that after being crosslinked by EDC, obtained carboxymethyl chitosan self-crosslinking polymer solubility property is good, with not handing over
Carboxymethyl chitosan (C-Chitosan) solution of connection is compared, and appearance is not much different.Carboxymethyl chitosan self-crosslinking obtained gathers
The infrared spectrum of object is closed as shown in compound C-C-C-1 in Fig. 1, from figure 1 it appears that carboxymethyl chitosan is crosslinked
Reaction.
2nd, application of the carboxymethyl chitosan self-crosslinking polymer prepared in lithium ion battery silicium cathode：
1) the carboxymethyl chitosan self-crosslinking polymer hydrogel of preparation is compared into nano-silicon according to quality：Conductive black：Carboxylic
Methyl chitosan self-crosslinking polymer=8:1:1 configuration, and ball milling and ultrasonic vibration are uniformly mixed, and slurry is made.
2) slurry obtained by step 1) is coated on copper foil, after being dried in vacuo 10 hours under the conditions of 60 DEG C, through roll-in backlash
Piece obtains a diameter of 14mm circles pole piece.By the way that density of the coating blade height control silicon nanoparticle on copper foil is controlled to be
1mg/cm2。
3) 100 DEG C of gained pole piece in step 2) is dried in vacuo after thoroughly removing moisture, in the glove box full of argon gas
It is comparison electrode with lithium piece, 1M LiPF6(FEC：DMC=1：1, V/V) it is electrolyte, 3501 diaphragms of Celgard are diaphragm group
Fill half-cell.
The lithium ion half-cell of assembling sets electric current using the charge-discharge performance of LAND-CT2001A testers detection battery
Density is 200mAg-1, setting voltage range is 0.02V~1.5V.
The half-cell of assembling is in 200mAg-1Current density under for the first time discharge capacity can reach 1967mAhg-1, cycle 100
Reversible capacity after secondary is 1093mAhg-1, relatively uncrosslinked carboxymethyl chitosan is as binding agent, reversible capacity for the first time
It is significantly improved, and cyclical stability will be got well.
Comparative example 1
1st, the preparation of carboxymethyl chitosan self-crosslinking polymer：
1) 164mg carboxymethyl chitosans (C-chitosan) are dissolved in the C-chitosan that 1wt% is configured in deionized water
Solution.
2) above-mentioned acquired solution is sequentially added into 1mL 0.5mol.L-1EDC and 2mL 1mol.L-1NHS (N- hydroxysuccinimidyls
Acid imide) solution, reacts 24 hours at room temperature；Control the pH value of solution left for 5.5 by adding in appropriate NaOH and HCl solution
It is right.
3) reaction product mixture obtained by step 2) is subjected to dialysis purification, MWCO=3.5kDa is set to remove in reaction
The small molecule of generation, obtain carboxymethyl chitosan self-crosslinking polymer hydrogel to get.
The dissolubility of the carboxymethyl chitosan self-crosslinking polymer of preparation is as shown in compound C-C-C-2 in Fig. 2, from figure
As can be seen that after being crosslinked by excessive EDC, obtained carboxymethyl chitosan self-crosslinking polymer solubility property is relatively
Difference illustrates that cross-linking reaction is excessive, and water soluble group is reduced, and causes water-soluble relatively poor.Carboxymethyl chitosan obtained is certainly
The infrared spectrum of cross-linked polymer is as shown in compound C-C-C-2 in Fig. 1.
2nd, application of the carboxymethyl chitosan self-crosslinking polymer prepared in lithium ion battery silicium cathode：
1) the carboxymethyl chitosan self-crosslinking polymer hydrogel of preparation is compared into nano-silicon according to quality：Conductive black：Carboxylic
Methyl chitosan self-crosslinking polymer=8:1:1 configuration, and ball milling and ultrasonic vibration are uniformly mixed, and slurry is made.
2) slurry obtained by step 1) is coated on copper foil, after being dried in vacuo 10 hours under the conditions of 60 DEG C, through roll-in backlash
Piece obtains a diameter of 14mm circles pole piece.By the way that density of the coating blade height control silicon nanoparticle on copper foil is controlled to be
1mg/cm2。
3) 100 DEG C of gained pole piece in step 2) is dried in vacuo after thoroughly removing moisture, in the glove box full of argon gas
It is comparison electrode with lithium piece, 1M LiPF6(FEC：DMC=1：1, V/V) it is electrolyte, 3501 diaphragms of Celgard are diaphragm group
Fill half-cell.
The lithium ion half-cell of assembling sets electric current using the charge-discharge performance of LAND-CT2001A testers detection battery
Density is 200mAg-1, setting voltage range is 0.02V~1.5V.
The half-cell of assembling is in 200mAg-1Current density under for the first time discharge capacity be 754mAhg-1, but recycle 80 and take second place
Reversible capacity afterwards is reduced to 300mAhg-1, relatively uncrosslinked carboxymethyl chitosan cyclical stability is poor；Illustrate excessively to hand over
After connection, carboxyl and hydroxyl that carboxymethyl chitosan self-crosslinking polymer contains largely reduce, can selfreparing with silicon face generation
Chemical number of keys reduce, self-repairing capability be deteriorated, cycle performance be deteriorated.
Comparison implements 2
1st, the preparation of carboxymethyl chitosan self-crosslinking polymer：
1) C-chitosan that 50mg carboxymethyl chitosans (C-chitosan) are dissolved in configuration 2wt% in deionized water is molten
Liquid.
2) above-mentioned acquired solution is sequentially added into 1.5mL 0.5mol.L-1EDC and 3mL 1mol.L-1NHS solution, in room
The lower reaction of temperature 24 hours；It is 5.5 or so by the pH value for adding in appropriate NaOH and HCl solution control solution.
3) reaction product mixture obtained by step 2) is subjected to dialysis purification, MWCO=3.5kDa is set to remove in reaction
The small molecule of generation, obtain carboxymethyl chitosan self-crosslinking polymer hydrogel to get.
The dissolubility of the carboxymethyl chitosan self-crosslinking polymer of preparation is as shown in compound C-C-C-3 in Fig. 2, from figure
As can be seen that after being crosslinked by excessive EDC, obtained carboxymethyl chitosan self-crosslinking polymer solubility property is relatively more
Difference is easily layered from water and is precipitated, illustrates that cross-linking reaction is excessive, and water soluble group is reduced, and causes water-soluble relatively poor.System
The infrared spectrum of the carboxymethyl chitosan self-crosslinking polymer obtained is as shown in compound C-C-C-3 in Fig. 1.
2nd, application of the carboxymethyl chitosan self-crosslinking polymer prepared in lithium ion battery silicium cathode：
1) the carboxymethyl chitosan self-crosslinking polymer hydrogel of preparation is compared into nano-silicon according to quality：Conductive black：Carboxylic
Methyl chitosan self-crosslinking polymer=8:1:1 configuration, and ball milling and ultrasonic vibration are uniformly mixed, and slurry is made.
2) slurry obtained by step 1) is coated on copper foil, after being dried in vacuo 10 hours under the conditions of 60 DEG C, through roll-in backlash
Piece obtains a diameter of 14mm circles pole piece.By the way that density of the coating blade height control silicon nanoparticle on copper foil is controlled to be
1mg/cm2。
3) 100 DEG C of gained pole piece in step 2) is dried in vacuo after thoroughly removing moisture, in the glove box full of argon gas
It is comparison electrode with lithium piece, 1M LiPF6(FEC：DMC=1:1, V/V) it is electrolyte, Celgard3501 diaphragms are assembled for diaphragm
Half-cell.
The lithium ion half-cell of assembling sets electric current using the charge-discharge performance of LAND-CT2001A testers detection battery
Density is 200mAg-1, setting voltage range is 0.02V~1.5V.
The half-cell of assembling is in 200mAg-1Current density under for the first time reversible capacity can reach 1800mAhg-1, cycle 80
Reversible capacity after secondary is 300mAhg-1；Compared with comparison implements 2, crosslinking degree further increases, and cycle performance does not have substantially
There is too big variation.
Comparative example 3
Directly using carboxymethyl chitosan as binding agent.Its solubility property is as shown such as (C-C) in Fig. 2.By the side of embodiment 1
Method prepares lithium ion battery silicon negative plate, and is assembled into lithium ion battery, is tested.
The lithium ion half-cell of assembling sets electric current using the charge-discharge performance of LAND-CT2001A testers detection battery
Density is 200mAg-1, setting voltage range is 0.02V~1.5V.
The half-cell of assembling is in 200mAg-1Current density under for the first time reversible capacity can reach 1300mAhg-1, cycle 100
Reversible capacity later is 980mAhg-1；As shown in (C-C) in Fig. 3；It can be seen from the figure that uncrosslinked carboxymethyl chitosan
The a large amount of carboxyl and hydroxyl contained, with silicon face generation can selfreparing chemical number of keys it is more, self-repairing capability compared with
By force, cycle performance is relatively good；But reversible capacity and the relatively appropriate crosslinked carboxymethyl chitosan of cycle performance are poor for the first time.
Comparative example 4
Carboxymethyl chitosan self-crosslinking polymer (C-C-C-1) prepared by embodiment 1 carries out battery assembling：
The carboxymethyl chitosan self-crosslinking polymer hydrogel of preparation is compared into nano-silicon according to quality：Conductive black：Carboxylic first
Base enclosure glycan self-crosslinking polymer=6:2:2 prepare, and prepare lithium ion battery silicon negative plate as described in Example 1.Assembling
For lithium ion half-cell using the charge-discharge performance of LANDCT2001A testers detection battery, setting current density is 200mAg-1,
Setting voltage range is 0.02V~1.5V.Capacity retention ratio maintains an equal level (1127mAh g-1) shown in (such as Fig. 4), cross-linked polymer table
Good adhesive property is shown, but more relatively poor than the silicium cathode performance of the preparation of the embodiment of the present invention 1.
Claims (7)
1. a kind of application of carboxymethyl chitosan self-crosslinking polymer in lithium ion battery, it is characterised in that：By carboxymethyl shell
Glycan self-crosslinking polymer is applied to prepare lithium ion battery silicium cathode as binding agent；
The carboxymethyl chitosan self-crosslinking polymer is prepared via a method which to obtain：Add in carboxymethyl chitosan solution
Entering 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides and n-hydroxysuccinimide, the pH value for controlling solution is 5~7,
At a temperature of 20~40 DEG C carry out cross-linking reaction to get；
1- (3- the dimethylamino-propyls) -3- ethyl carbodiimides addition for carboxymethyl chitosan mole 10~
20%.
2. application of the carboxymethyl chitosan self-crosslinking polymer according to claim 1 in lithium ion battery, feature
It is：Cross-linking reaction time is 20~25h.
3. application of the carboxymethyl chitosan self-crosslinking polymer according to claim 1 or 2 in lithium ion battery, special
Sign is：The carboxymethyl chitosan self-crosslinking polymer molecular weight is more than 3.5kDa.
4. application of the carboxymethyl chitosan self-crosslinking polymer according to claim 1 in lithium ion battery, feature
It is：Lithium ion battery silicium cathode is prepared by the raw material including following mass percent component：Silicon materials 70~
90%, conductive agent 5~15%, the binding agent 5~15%.
5. application of the carboxymethyl chitosan self-crosslinking polymer according to claim 4 in lithium ion battery, feature
It is：The binding agent quality is the 10~15% of silicon materials quality.
6. application of the carboxymethyl chitosan self-crosslinking polymer according to claim 4 in lithium ion battery, feature
It is：The silicon materials are nano-silicon.
7. application of the carboxymethyl chitosan self-crosslinking polymer according to claim 4 in lithium ion battery, feature
It is：The conductive agent is at least one of carbon nanotube, superconduction carbon black, graphite, high electric conductivity carbon, graphene.
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| CN107482221B (en) * | 2017-07-05 | 2019-12-24 | 长沙理工大学 | Polymer crosslinked binder and preparation method and application thereof |
| TWI631754B (en) * | 2017-07-07 | 2018-08-01 | 聚和國際股份有限公司 | The 3d network structure binder and the anode materials included it for lithium ion batteries |
| CN109216699B (en) * | 2017-07-07 | 2022-04-19 | 聚和国际股份有限公司 | Lithium battery adhesive with three-dimensional structure and lithium battery negative electrode material containing same |
| CN107419530B (en) * | 2017-07-26 | 2020-01-14 | 武汉理工大学 | Polycaprolactone electrostatic spinning stent and preparation method thereof |
| CN108461691B (en) * | 2018-02-08 | 2019-05-10 | 深圳锂硫科技有限公司 | A kind of lithium-sulfur cell diaphragm and preparation method thereof |
| CN108832126B (en) * | 2018-04-25 | 2021-07-20 | 华南理工大学 | Polycarboxylic acid aqueous binder containing coupling amido bond, preparation method and application thereof in lithium ion battery |
| CN109244468A (en) * | 2018-08-02 | 2019-01-18 | 合肥国轩高科动力能源有限公司 | Modified chitosan negative electrode binder and preparation method of negative electrode sheet containing binder |
| CN109686980A (en) * | 2018-12-15 | 2019-04-26 | 华南理工大学 | A kind of lithium ion battery with high energy density |
| CN110970622A (en) * | 2019-12-18 | 2020-04-07 | 陕西煤业化工技术研究院有限责任公司 | Water-based binder and preparation method and application thereof |
| CN110931261B (en) * | 2019-12-18 | 2021-10-29 | 中原工学院 | Preparation method of flexible fabric supercapacitor electrode material with graphene/polypyrrole as active substance |
| CN111063891B (en) * | 2019-12-23 | 2022-08-30 | 浙江中科立德新材料有限公司 | Preparation method of aqueous conductive adhesive |
| CN113555540A (en) * | 2021-07-21 | 2021-10-26 | 凤凰新能源(惠州)有限公司 | Fast-charging polymer lithium ion battery |
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