CN105702963A - Application of carboxymethyl chitosan self-crosslinking polymer in silicon negative electrode of lithium ion battery - Google Patents
Application of carboxymethyl chitosan self-crosslinking polymer in silicon negative electrode of lithium ion battery Download PDFInfo
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- H01M10/05—Accumulators with non-aqueous electrolyte
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Abstract
The invention discloses an application of a carboxymethyl chitosan self-crosslinking polymer in a silicon negative electrode of a lithium ion battery. The carboxymethyl chitosan self-crosslinking polymer is obtained by adding carboxymethyl chitosan to cross-liking agent 1-(3-(dimethylamino propyl)-3-ethyl-carbodiimide hydrochloride in a self-crosslinking manner; the polymer has a three-dimensional structure, and is taken as a binder to be applied to preparation of the silicon negative electrode of the lithium ion battery; the self-crosslinking polymer shows high mechanical performance and adhesive property; chemical bonds with self-repairing capability are formed between the self-crosslinking polymer and the silicon particles; the silicon negative electrode with large volume change in the charging-discharging process can be effectively accommodated; the powder-fall-off phenomenon with structural damage caused by severe volume changes of the silicon particles in the circulating process of the silicon negative electrode is solved; and a new approach for improving the cycle performance of the silicon negative electrode of the lithium ion battery is provided.
Description
Technical field
The present invention relates to a kind of carboxymethyl chitosan self-crosslinking polymer in lithium ion battery as the application of silicium cathode binding agent, it is specifically related to the preparation of a kind of modification biological natural polymer binding agent and the application in lithium battery silicium cathode thereof, relates to technical field of lithium batteries。
Background technology
Along with the development of mancarried electronic aid and electric automobile, the requirement of the energy density of lithium battery is also being improved by people day by day。In order to improve the energy density of lithium battery, the performance of its each ingredient (positive pole, negative pole, electrolyte and barrier film) is all to be improved。In negative material, traditional negative material graphite is due to its relatively low theoretical capacity (372mAhg-1) can not meet the requirement of high-energy-density, the researcher research pay attention to day by day to height ratio capacity negative material。IV race elemental silicon has the theoretical capacity (4200mAhg of superelevation due to it-1) become the focus of lithium ion battery negative material area research of future generation。But nano-silicon as negative material have the drawback that battery in charge and discharge process owing to the deintercalation of a large amount of lithium ions causes violent volumetric expansion (300%), change in volume repeatedly in cyclic process, to progressively lose between silicon with other components and be connected, make nano-silicon lose electronics with conductive agent to contact, and come off from collector, cause that battery capacity decays。
In order to improve performance and its cycle life of silicium cathode, researcheres report prepare silica-based multi-element composite material, control silicon grain diameter, improve slurry spraying technology, the methods such as high-performance adhesive are prepared in design。Wherein, between intensifier electrode, the interaction of each component is to solve silicium cathode material capacity attenuation effective approach rapidly in cyclic process。Suitable high-performance adhesive is selected then to be to increase in electrode one of effective way of interaction of each component。Easily there is plastic deformation in conventional binding agent Kynoar (PVDF), when silicium cathode change in volume is bigger, nano-silicon and conductive agent easily fill on pole piece and come off when for silicium cathode due to PVDF。And due to the shortcoming such as its dispersant N-Methyl pyrrolidone (NMP) is expensive and poisonous, the research of novel binders is particularly important。At present。The subject matter that silicium cathode binding agent presently, there are is: (1) adhesive property is not strong, it is impossible to and produce strong interaction between active substance and other components；(2) expensive raw material price, complicated process of preparation, it is not suitable for large-scale production；(3) preparation process is easily generated environmental pollution, does not meet the requirement of green production。
Biomaterial, as a kind of Renewable resource, wide material sources, has been used for every field。2011, Kovalenko etc. reported sodium alginate application (Science, 334 (2011) 75) in silicium cathode。When silicium cathode uses the water soluble polymer sodium alginate extracted from Brown algae as binding agent, at 4200mAg-1The reversible capacity after 100 times is circulated more than 1700mAhg under electric current-1, and use PVDF as the silicium cathode reversible capacity under the same conditions of binding agent already close to zero。Liu etc. are using biopolymer guar gum GG) it is used in silicium cathode (AdvancedFunctionalMaterials, 25 (2015) 3599) as binding agent。Research shows, the GG with substantial amounts of polar functional group can form higher interaction with silicon atom surface, and GG can improve the electric conductivity of pole piece simultaneously。
The polymer of hydroxyl and carboxyl is to study a most commonly used class binding agent in silicium cathode。Hydroxy functional group has hydrophilic, and therefore the polymeric binder of hydroxyl is generally dissolved in water, and this kind of binding agent can use water as dispersant and produce for pole piece thus avoiding the environmental pollution using organic solvent to cause as dispersant。Carboxyl functional group can and silicon dioxide (being present in silicon atom surface) and copper (or oxide of copper) between generate the hydrogen bond with strong interaction。And, it was reported that the hydrogen bond generated between them has self-reparing capability, can be spontaneous after destroyed carry out self-regeneration。Therefore, relative to the polymeric binder (such as PVDF, styrene-dibutene rubber (SBR)) without carboxyl functional group, polymeric binder and derivant (such as sodium alginate, polyacrylic acid (PAA), carboxymethyl cellulose (CMC), carboxymethyl chitosan etc.) thereof containing hydroxyl or carboxyl functional group show better chemical property for silicium cathode。
Chitosan is the modified product of the chitin in Crusta Penaeus seu Panulirus, and it contains abundant hydroxyl。Zheng etc. report and as binding agent, chitosan are used for graphite cathode (ElectrochimicaActa, 105 (2013) 378), relatively existing binder material, can improve the cycle performance of pole piece to a certain extent。It addition, carboxymethyl chitosan is used as silicium cathode binder phase by Yue etc., and existing binding agent also illustrates good performance (JournalOfPowerSources, 247 (2014) 327)；Although carboxymethyl chitosan can utilize its a large amount of carboxyls contained and hydroxyl and silicon face to form the hydrogen bond with certain self-healing properties, improve the cycle performance of silicium cathode；But, the self-repairing capability relying on hydrogen bond is limited, cannot thoroughly solve in charge and discharge process owing to the deintercalation of a large amount of lithium ions causes violent volumetric expansion, and cause in cyclic process change in volume repeatedly, to progressively lose between silicon with other components and be connected, make nano-silicon lose electronics with conductive agent to contact, and come off from collector, cause the defect that battery capacity decays。
Current research finds, 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, is expected to improve cycle performance and the effective ratio capacity of negative pole。Jeong etc. report hyperbranched beta cyclo dextrin polymer (β-CDp) as lithium ion battery Si negative electrode binder (NanoLetters, 14 (2014) 864)。Being found by peel test, using β-CDp tightr as binding agent relative to using sodium alginate as each component of the pole piece of binding agent, bond effect is better。They point out, relative to the linear structure of sodium alginate, the tridimensional network of β-CDp can effectively suppress Si granule change in volume in charge and discharge process。At 1C (4200mAg-1) under electric current density after circulation 150 times, the capability retention of the pole piece using β-CDp and the pole piece using sodium alginate respectively 50.6% and 27.1%, and use PVDF just to lose efficacy after 10 circulations as the Si negative pole of binding agent。
Song etc. obtain a kind of new gelatin polymer binding agent by in-situ cross-linked mode cross linked polyacrylate (PAA) and polyvinyl alcohol (PVA)。The network structure of this gel polymer electrolyte can effectively cushion the lithium battery violent change in volume that silicon grain causes when high current charge-discharge due to the deintercalation of lithium ion, uses the capacity per unit area of PAA-PVA polymer gel binding agent can reach 4.3mAh/cm2(AdvancedFunctionalMaterials.24 (2014) 5904-5910)。Gel effect can be effectively improved the rheological property of slurry。The crosslinking degree of the gelatin polymer binding agent that use this method obtains fails to obtain quantitative control, and therefore the performance of the silicium cathode that this binding agent prepares is also unstable。
Koo etc. use PAA and CMC to obtain a kind of three-dimensional polymer binding agent by polycondensation reaction。Use the silicium cathode of this binding agent at 175mAg-1Reversible capacity after circulating 100 times under electric current density reaches 2000mAhg-1, at 30Ag-1Electric current density, reversible capacity at 60 DEG C of temperature is up to 1500mAhg-1。(AngewandteChemie-InternationalEdition.51 (2012) 8762-8767)。Liu etc. report mixed and modified as Si negative electrode binder (ElectrochemicalAndSolidStateLetters, 8 (2005) A100) to styrene butadiene ribber (SBR) and the Na-CMC of elastomer。This hybrid adhesive can improve mechanical property and the pole piece swelling behavior in the electrolytic solution of pole piece。But owing to the compatibility between SBR and Na-CMC is not very well, the performance of this hybrid adhesive need to improve。
Japan Patent (JP2003282061) and (JP2006215761) etc. propose and use the mode of nitrile rubber or butadiene and fluoro containing polymers mechanical blending to produce a kind of high-performance adhesive。Although the pliability of binding agent and caking property are enhanced, but physical mechanical is blended to be formed owing to it adopts, so binding agent internal mix obtains uniform not, the slurry configured there will be lamination after the standing。Owing to not interacting between two kinds of polymer, pole piece in use can produce segregation phenomenon, affects the cycle performance of pole piece。
China Dongfang Electric Group Corporation discloses the preparation method (CN201110427929) of a kind of Compound Water soluble binder。The method utilizes amorphous poly ethylene oxide base polymer aqueous solution and gel-type water-soluble binder to carry out block polymerization and obtain。This binding agent has good compliance, improves the pliability of pole piece, the advantage simultaneously combining two kinds of water soluble polymers, improves capacity and the cycle performance of pole piece。But the preparation process of this binding agent is more complicated, and the pole piece performance boost being worth inconspicuous。Hubei Wanrun New Energy Technology Development Co., Ltd. discloses preparation method and the application (CN201310364057) of a kind of compound binding agent。The macromolecule of a kind of macromolecule containing carboxyl functional group with a kind of hydroxy functional groups is formed by the method by adding cross-linking agent heat cross-linking, and obtained binding agent has good plasticity and adhesive property。This invention must take into the compatibility and the ratio problems of two kinds of polymer in the preparation。
Summary of the invention
There is the problems such as adhesive property difference, complicated process of preparation, self-repair function difference for polymeric binder in prior art, and existing lithium battery silicium cathode materials application requirement cannot be met, it is an object of the invention to the application being in that to provide a kind of carboxymethyl chitosan self-crosslinking polymer with 3-D solid structure, this cross linked polymer shows good mechanical performance, adhesive property and chemical bond self-reparing capability, can effectively solve the silicium cathode structural damage that silicon grain causes in cyclic process due to violent change in volume。
In order to realize above-mentioned technical purpose, the invention provides the application of a kind of carboxymethyl chitosan self-crosslinking polymer, be applied to prepare lithium ion battery silicium cathode as binding agent using carboxymethyl chitosan self-crosslinking polymer；
Described carboxymethyl chitosan self-crosslinking polymer is obtained by cross-linking reaction with 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide (EDC) by carboxymethyl chitosan。
Preferred scheme, carboxymethyl chitosan self-crosslinking polymer is prepared via a method which to obtain: adding EDC and N-hydroxy-succinamide in carboxymethyl chitosan solution, the pH value controlling solution is 5～7, carries out cross-linking reaction, to obtain final product at 20～40 DEG C of temperature。
Preferred scheme, the addition of EDC is the 10～30% of carboxymethyl chitosan mole；It is more preferably 10～20%。
Preferred scheme, cross-linking reaction time is 20～25h。
Preferred scheme, carboxymethyl chitosan self-crosslinking polymer molecular weight is more than 3.5kDa。
Preferred scheme, lithium ion battery silicium cathode is prepared by the raw material including following mass percent component: silicon materials 70～90%, conductive agent 5～15%, described binding agent 5～15%。
Preferred scheme, the quality of binding agent is the 10～15% of silicon materials quality。
Preferred scheme, silicon materials are nano-silicon。
Preferred scheme, conductive agent is at least one in CNT, superconduction white carbon black, graphite, high electric conductivity carbon, Graphene。
More preferably scheme, cross-linking reaction time is 20～25h。
More preferably scheme, cross-linking reaction gained mixed solution carries out dialysis treatment by ultrafilter membrane, and the molecular cut off of ultrafilter membrane is 3.5kDa。
The carboxymethyl chitosan self-crosslinking polymer of the present invention is prepared by following steps:
(1) carboxymethyl chitosan is dissolved in deionized water configure 1～2wt% carboxymethyl chitosan solution；
(2), after being sequentially added in carboxymethyl chitosan solution by 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide and N-hydroxy-succinamide, regulating pH value is 5～7, reacts 20～30 hours under room temperature environment；
(3) product of above-mentioned gained is placed in deionized water to dialyse purification 1～3 day, removes the molecular weight molecular weight polymers less than 3.5kDa and small molecule by-product, obtain binding agent hydrogel。
The N-hydroxy-succinamide adopted in the solution of the present invention is used for improving cross-linking efficiency。
Compared with prior art, the invention have the benefit that
(1) technical scheme modifiies by carboxymethyl chitosan carries out self-crosslinking, what obtain has the cancellated carboxymethyl chitosan self-crosslinking polymer of multidimensional, it is low that it has good mechanical performance, degree of crystallinity, and introduce partial amides key by EDC crosslinking and itself contain great amount of hydroxy group, carboxyl and amino, and the active force between silicon materials and collector is strong, can play good cementation。
(2) the carboxymethyl chitosan self-crosslinking polymer of the present invention makes full use of its multidimensional network structure, can effectively hold the silicium cathode large volume caused change in charge and discharge process, solve the silicium cathode structural damage that silicon grain causes due to violent change in volume in cyclic process。
(3) the carboxymethyl chitosan self-crosslinking polymer of the present invention remains appropriate carboxyl and hydroxyl and amino, and water solublity is better, can with silicon face generate can the chemical bond of selfreparing, be effectively improved the cycle performance of pole piece。
(4) requirement of preparation process composite green safety in production, simple to operate, it is easy to controls, and feasibility is high, is suitable for industrial-scale production。
Accompanying drawing explanation
[Fig. 1] is the infrared spectrogram of the carboxymethyl chitosan of the different self-crosslinking degree of embodiment 1 and comparative example 1～3；
[Fig. 2] is the solution thereon of the carboxymethyl chitosan of the different self-crosslinking degree of embodiment 1 and comparative example 1～3；
The cycle performance comparison diagram of the silicium cathode that [Fig. 3] prepares as binding agent for the different carboxymethyl chitosan self-crosslinking polymer of embodiment 1 and comparative example 1～3；
The cycle performance figure of the silicium cathode that [Fig. 4] prepares for adopting carboxymethyl chitosan self-crosslinking polymer in comparative example 4。
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further, but the claims in the present invention protection domain is not constituted any restriction, is only adapted to assist in and understands present invention。
Embodiment 1
1, the preparation of carboxymethyl chitosan self-crosslinking polymer:
1) it is dissolved in deionized water by 164mg carboxymethyl chitosan (C-chitosan) configuring the C-chitosan solution of 1wt%。
2) above-mentioned gained solution is sequentially added into 0.5mL0.5mol.L-1EDC (molal quantity is about the 17% of carboxymethyl chitosan) and 1mol.L-1NHS solution, at room temperature reaction 24 hours；It is about 5.5 by adding the pH value of appropriate NaOH and HCl solution control solution。
3) by step 2) reaction product mixture of gained carries out dialysis purification, and MWCO=3.5kDa is set to remove the little molecule of generation in reaction, obtains carboxymethyl chitosan self-crosslinking polymer hydrogel, to obtain final product。
In dissolubility such as Fig. 2 of the carboxymethyl chitosan self-crosslinking polymer of preparation shown in compound C-C-C-1, as can be seen from Figure 2, after being cross-linked by EDC, the carboxymethyl chitosan self-crosslinking polymer solubility property obtained is good, compared with uncrosslinked carboxymethyl chitosan (C-Chitosan) solution, outward appearance is more or less the same。In the infrared spectrum such as Fig. 1 of the carboxymethyl chitosan self-crosslinking polymer prepared shown in compound C-C-C-1, from figure 1 it appears that carboxymethyl chitosan has carried out cross-linking reaction。
2, the carboxymethyl chitosan self-crosslinking polymer of preparation application in lithium ion battery silicium cathode:
1) by the carboxymethyl chitosan self-crosslinking polymer hydrogel of preparation according to quality than nano-silicon: conductive black: carboxymethyl chitosan self-crosslinking polymer=8:1:1 configuration, and ball milling and ultrasonic vibration mix homogeneously, make slurry。
2) by step 1) gained slurry is coated on Copper Foil, and under 60 DEG C of conditions, vacuum drying is after 10 hours, and after roll-in, punching obtains diameter is 14mm circle pole piece。It is 1mg/cm by controlling coating blade Altitude control silicon nanoparticle density on Copper Foil2。
3) by step 2) in after 100 DEG C of vacuum dryings of gained pole piece thoroughly remove moisture, be comparison electrode with lithium sheet in the glove box of full argon, 1MLiPF6(FEC:DMC=1:1, V/V) is electrolyte, and Celgard3501 barrier film is that barrier film assembles half-cell。
The lithium ion half-cell assembled uses the charge-discharge performance of LAND-CT2001A tester detection battery, and arranging electric current density is 200mAg-1, arranging voltage range is 0.02V～1.5V。
The half-cell assembled is at 200mAg-1Electric current density under first discharge capacity can reach 1967mAhg-1, circulating the reversible capacity after 100 times is 1093mAhg-1, its relatively uncrosslinked carboxymethyl chitosan is as binding agent, and reversible capacity is significantly improved first, and cyclical stability to be got well。
Comparative example 1
1, the preparation of carboxymethyl chitosan self-crosslinking polymer:
1) it is dissolved in deionized water by 164mg carboxymethyl chitosan (C-chitosan) configuring the C-chitosan solution of 1wt%。
2) above-mentioned gained solution is sequentially added into 1mL0.5mol.L-1EDC and 2mL1mol.L-1NHS (N-hydroxy-succinamide) solution, at room temperature reaction 24 hours；It is about 5.5 by adding the pH value of appropriate NaOH and HCl solution control solution。
3) by step 2) reaction product mixture of gained carries out dialysis purification, and MWCO=3.5kDa is set to remove the little molecule of generation in reaction, obtains carboxymethyl chitosan self-crosslinking polymer hydrogel, to obtain final product。
In dissolubility such as Fig. 2 of the carboxymethyl chitosan self-crosslinking polymer of preparation shown in compound C-C-C-2, as can be seen from the figure, after being cross-linked by excessive EDC, the carboxymethyl chitosan self-crosslinking polymer solubility property obtained is relatively poor, explanation cross-linking reaction is excessive, its water soluble group reduces, and causes that water solublity is relatively poor。In the infrared spectrum such as Fig. 1 of the carboxymethyl chitosan self-crosslinking polymer prepared shown in compound C-C-C-2。
2, the carboxymethyl chitosan self-crosslinking polymer of preparation application in lithium ion battery silicium cathode:
1) by the carboxymethyl chitosan self-crosslinking polymer hydrogel of preparation according to quality than nano-silicon: conductive black: carboxymethyl chitosan self-crosslinking polymer=8:1:1 configuration, and ball milling and ultrasonic vibration mix homogeneously, make slurry。
2) by step 1) gained slurry is coated on Copper Foil, and under 60 DEG C of conditions, vacuum drying is after 10 hours, and after roll-in, punching obtains diameter is 14mm circle pole piece。It is 1mg/cm by controlling coating blade Altitude control silicon nanoparticle density on Copper Foil2。
3) by step 2) in after 100 DEG C of vacuum dryings of gained pole piece thoroughly remove moisture, be comparison electrode with lithium sheet in the glove box of full argon, 1MLiPF6(FEC:DMC=1:1, V/V) is electrolyte, and Celgard3501 barrier film is that barrier film assembles half-cell。
The lithium ion half-cell assembled uses the charge-discharge performance of LAND-CT2001A tester detection battery, and arranging electric current density is 200mAg-1, arranging voltage range is 0.02V～1.5V。
The half-cell assembled is at 200mAg-1Electric current density under first discharge capacity be 754mAhg-1, but the reversible capacity after circulating 80 times is reduced to 300mAhg-1, relatively uncrosslinked carboxymethyl chitosan cyclical stability is poor；After excessively crosslinking is described, carboxyl and hydroxyl that carboxymethyl chitosan self-crosslinking polymer contains reduce in a large number, itself and silicon face generate can the chemical bond decreased number of selfreparing, self-repairing capability is deteriorated, and cycle performance is deteriorated。
Contrast enforcement 2
1, the preparation of carboxymethyl chitosan self-crosslinking polymer:
1) it is dissolved in deionized water by 50mg carboxymethyl chitosan (C-chitosan) configuring the C-chitosan solution of 2wt%。
2) above-mentioned gained solution is sequentially added into 1.5mL0.5mol.L-1EDC and 3mL1mol.L-1NHS solution, at room temperature reaction 24 hours；It is about 5.5 by adding the pH value of appropriate NaOH and HCl solution control solution。
3) by step 2) reaction product mixture of gained carries out dialysis purification, and MWCO=3.5kDa is set to remove the little molecule of generation in reaction, obtains carboxymethyl chitosan self-crosslinking polymer hydrogel, to obtain final product。
In dissolubility such as Fig. 2 of the carboxymethyl chitosan self-crosslinking polymer of preparation shown in compound C-C-C-3, as can be seen from the figure, after being cross-linked by excessive EDC, the carboxymethyl chitosan self-crosslinking polymer solubility property obtained is relatively worse, easily from water, layering precipitates out, explanation cross-linking reaction is excessive, and its water soluble group reduces, and causes that water solublity is relatively poor。In the infrared spectrum such as Fig. 1 of the carboxymethyl chitosan self-crosslinking polymer prepared shown in compound C-C-C-3。
2, the carboxymethyl chitosan self-crosslinking polymer of preparation application in lithium ion battery silicium cathode:
1) by the carboxymethyl chitosan self-crosslinking polymer hydrogel of preparation according to quality than nano-silicon: conductive black: carboxymethyl chitosan self-crosslinking polymer=8:1:1 configuration, and ball milling and ultrasonic vibration mix homogeneously, make slurry。
2) by step 1) gained slurry is coated on Copper Foil, and under 60 DEG C of conditions, vacuum drying is after 10 hours, and after roll-in, punching obtains diameter is 14mm circle pole piece。It is 1mg/cm by controlling coating blade Altitude control silicon nanoparticle density on Copper Foil2。
3) by step 2) in after 100 DEG C of vacuum dryings of gained pole piece thoroughly remove moisture, be comparison electrode with lithium sheet in the glove box of full argon, 1MLiPF6(FEC:DMC=1:1, V/V) is electrolyte, and Celgard3501 barrier film is that barrier film assembles half-cell。
The lithium ion half-cell assembled uses the charge-discharge performance of LAND-CT2001A tester detection battery, and arranging electric current density is 200mAg-1, arranging voltage range is 0.02V～1.5V。
The half-cell assembled is at 200mAg-1Electric current density under first reversible capacity can reach 1800mAhg-1, circulating the reversible capacity after 80 times is 300mAhg-1；Implementing compared with in the of 2 with contrast, crosslinking degree strengthens further, and its cycle performance is substantially free of too big change。
Comparative example 3
Directly using carboxymethyl chitosan as binding agent。In its solubility property such as Fig. 2 shown in (C-C)。Prepare lithium ion battery silicon negative plate by the method for embodiment 1, and be assembled into lithium ion battery, test。
The lithium ion half-cell assembled uses the charge-discharge performance of LAND-CT2001A tester detection battery, and arranging electric current density is 200mAg-1, arranging voltage range is 0.02V～1.5V。
The half-cell assembled is at 200mAg-1Electric current density under first reversible capacity can reach 1300mAhg-1, the reversible capacity after circulation 100 is 980mAhg-1；In Fig. 3 shown in (C-C)；It can be seen that the substantial amounts of carboxyl that contains of uncrosslinked carboxymethyl chitosan and hydroxyl, itself and silicon face generate can the chemical bond number of selfreparing more, self-repairing capability is relatively strong, and cycle performance is relatively good；But the carboxymethyl chitosan that reversible capacity and cycle performance suitably cross-link relatively first is poor。
Comparative example 4
The carboxymethyl chitosan self-crosslinking polymer (C-C-C-1) embodiment 1 prepared carries out battery assembling:
By the carboxymethyl chitosan self-crosslinking polymer hydrogel of preparation according to quality than nano-silicon: conductive black: carboxymethyl chitosan self-crosslinking polymer=6:2:2 preparation, prepare lithium ion battery silicon negative plate by the method for embodiment 1。The lithium ion half-cell assembled uses the charge-discharge performance of LANDCT2001A tester detection battery, and arranging electric current density is 200mAg-1, arranging voltage range is 0.02V～1.5V。Capability retention maintains an equal level (1127mAhg-1) shown in (such as Fig. 4), cross linked polymer represents good adhesive property, but more relatively poor than the silicium cathode performance of the preparation of embodiments of the invention 1。
Claims (10)
1. the carboxymethyl chitosan self-crosslinking polymer application in lithium ion battery, it is characterised in that: it is applied to prepare lithium ion battery silicium cathode as binding agent using carboxymethyl chitosan self-crosslinking polymer；
Described carboxymethyl chitosan self-crosslinking polymer is obtained by cross-linking reaction by carboxymethyl chitosan and 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide。
2. the carboxymethyl chitosan self-crosslinking polymer according to claim 1 application in lithium ion battery, it is characterized in that: described carboxymethyl chitosan self-crosslinking polymer is prepared via a method which to obtain: in carboxymethyl chitosan solution, add 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide and N-hydroxy-succinamide, the pH value controlling solution is 5～7, at 20～40 DEG C of temperature, carry out cross-linking reaction, to obtain final product。
3. the carboxymethyl chitosan self-crosslinking polymer according to claim 2 application in lithium ion battery, it is characterised in that: described 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide addition is the 10～30% of carboxymethyl chitosan mole。
4. the carboxymethyl chitosan self-crosslinking polymer according to claim 3 application in lithium ion battery, it is characterised in that: described 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide addition is the 10～20% of carboxymethyl chitosan mole。
5. the carboxymethyl chitosan self-crosslinking polymer according to claim 2 application in lithium ion battery, it is characterised in that: cross-linking reaction time is 20～25h。
6. the application in lithium ion battery of the carboxymethyl chitosan self-crosslinking polymer according to any one of Claims 1 to 5, it is characterised in that: described carboxymethyl chitosan self-crosslinking polymer molecular weight is more than 3.5kDa。
7. the carboxymethyl chitosan self-crosslinking polymer according to claim 1 application in lithium ion battery, it is characterized in that: lithium ion battery silicium cathode is prepared by the raw material including following mass percent component: silicon materials 70～90%, conductive agent 5～15%, described binding agent 5～15%。
8. the carboxymethyl chitosan self-crosslinking polymer according to claim 7 application in lithium ion battery, it is characterised in that: described binding agent quality is silicon materials quality 10～15%。
9. the carboxymethyl chitosan self-crosslinking polymer according to claim 7 application in lithium ion battery, it is characterised in that: described silicon materials are nano-silicon。
10. the carboxymethyl chitosan self-crosslinking polymer according to claim 7 application in lithium ion battery, it is characterised in that: described conductive agent is at least one in CNT, superconduction white carbon black, graphite, high electric conductivity carbon, Graphene。
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| CN107419530A (en) * | 2017-07-26 | 2017-12-01 | 武汉理工大学 | A kind of polycaprolactone electrospun scaffolds and preparation method thereof |
| CN107482221A (en) * | 2017-07-05 | 2017-12-15 | 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 |
| CN108461691A (en) * | 2018-02-08 | 2018-08-28 | 深圳锂硫科技有限公司 | A kind of lithium-sulfur cell diaphragm and preparation method thereof |
| CN108832126A (en) * | 2018-04-25 | 2018-11-16 | 华南理工大学 | A kind of polycarboxylic acids aqueous binders of the amido bond containing coupling and preparation method and its application in lithium ion battery |
| CN109216699A (en) * | 2017-07-07 | 2019-01-15 | 聚和国际股份有限公司 | Have the lithium battery adhesive agent of three-dimensional structure and the lithium cell cathode material containing it |
| CN109244468A (en) * | 2018-08-02 | 2019-01-18 | 合肥国轩高科动力能源有限公司 | A kind of chitosan negative electrode binder of modification and the preparation method of the negative electrode tab containing the 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 |
| CN110931261A (en) * | 2019-12-18 | 2020-03-27 | 中原工学院 | Preparation method of flexible fabric supercapacitor electrode material with graphene/polypyrrole as active substance |
| 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 |
| CN111063891A (en) * | 2019-12-23 | 2020-04-24 | 浙江中科立德新材料有限公司 | Water-based conductive adhesive and preparation method thereof |
| 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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| CN107482221B (en) * | 2017-07-05 | 2019-12-24 | 长沙理工大学 | Polymer crosslinked binder and preparation method and application thereof |
| CN107482221A (en) * | 2017-07-05 | 2017-12-15 | 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 |
| CN109216699A (en) * | 2017-07-07 | 2019-01-15 | 聚和国际股份有限公司 | Have the lithium battery adhesive agent of three-dimensional structure and the lithium cell cathode material containing it |
| 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 |
| CN107419530A (en) * | 2017-07-26 | 2017-12-01 | 武汉理工大学 | A kind of polycaprolactone electrospun scaffolds and preparation method thereof |
| CN108461691A (en) * | 2018-02-08 | 2018-08-28 | 深圳锂硫科技有限公司 | A kind of lithium-sulfur cell diaphragm and preparation method thereof |
| CN108832126A (en) * | 2018-04-25 | 2018-11-16 | 华南理工大学 | A kind of polycarboxylic acids aqueous binders of the amido bond containing coupling and preparation method and its application 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 | A kind of chitosan negative electrode binder of modification and the preparation method of the negative electrode tab containing the 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 |
| CN110931261A (en) * | 2019-12-18 | 2020-03-27 | 中原工学院 | Preparation method of flexible fabric supercapacitor electrode material with graphene/polypyrrole as active substance |
| 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 |
| CN111063891A (en) * | 2019-12-23 | 2020-04-24 | 浙江中科立德新材料有限公司 | Water-based conductive adhesive and preparation method thereof |
| 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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