CN106928882A - Sesbania gum water-based binder and its application in lithium ion battery negative - Google Patents
Sesbania gum water-based binder and its application in lithium ion battery negative Download PDFInfo
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- CN106928882A CN106928882A CN201710214843.5A CN201710214843A CN106928882A CN 106928882 A CN106928882 A CN 106928882A CN 201710214843 A CN201710214843 A CN 201710214843A CN 106928882 A CN106928882 A CN 106928882A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J105/00—Adhesives based on polysaccharides or on their derivatives, not provided for in groups C09J101/00 or C09J103/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0087—Glucomannans or galactomannans; Tara or tara gum, i.e. D-mannose and D-galactose units, e.g. from Cesalpinia spinosa; Tamarind gum, i.e. D-galactose, D-glucose and D-xylose units, e.g. from Tamarindus indica; Gum Arabic, i.e. L-arabinose, L-rhamnose, D-galactose and D-glucuronic acid units, e.g. from Acacia Senegal or Acacia Seyal; Derivatives thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The present invention relates to a kind of sesbania gum water-based binder and its application in lithium ion battery negative, lithium ion battery negative material is prepared using the sesbania gum and its derivative of formula 1, its constituent is by mass percentage active material:Conductive agent:Binding agent=（50‑80）:（10‑30）:（10‑20）.Sesbania gum system binding agent proposed by the invention is applied to lithium ion battery negative material and prepares electrode slice, and cycle performance of battery is improved, and uses new binding agent wide material sources, is the novel binders of environmental protection with water solubility.In view of the superperformance of silicium cathode, by the use of water-soluble sesbania gum and its derivative as battery binding agent, the commercialization process of implementation and promotion Si negative poles to the strategy of sustainable development undoubtedly has important effect.
Description
Technical field
The present invention relates to electrochemistry and novel energy resource material technology field, and in particular to a kind of sesbania gum water-based binder and its
Application in lithium ion battery negative.
Background technology
Lithium ion battery has energy density high, has extended cycle life, and is widely used to the advantages of environmental pollution is small all kinds of
Portable electric appts, also as power resources in growing electric automobile field.In lithium ion battery electrode material
Development process in, Si sills receive much concern because of the theoretical embedding lithium capacity (4200mAh/g) with highest.But Si base materials
There is serious bulk effect in material, cause the cyclical stability of electrode significantly to decline under the conditions of high level removal lithium embedded.For
The volume efficiency of silicon, selects suitable binding agent most important.
The content of the invention
It is an object of the invention to provide a kind of sesbania gum water-based binder and its application in lithium ion battery negative, generation
For traditional PVDF and CMC, there is provided a kind of new type lithium ion battery negative pole binding agent of environmental protection.
The technical solution adopted in the present invention is：
Sesbania gum water-based binder, it is characterised in that：
Described binding agent is the sesbania gum and its derivative shown in formula 1；
Formula 1
Wherein, R- is H or CH2COO-；
Dispersion is deionized water.
Described sesbania gum and its range of viscosities of derivative are 200-1300 mPa.s.
As mentioned sesbania gum water-based binder as lithium ion battery negative material binding agent application.
The constituent of the lithium ion battery negative material is by mass percentage：
Active material:Conductive agent:Binding agent=（50-80）:（10-30）:（10-20）；
Wherein, binding agent is the sesbania gum and its derivative shown in formula 1, and dispersion is deionized water；
Formula 1
Wherein, R- is H or CH2COO-。
The active material is selected from silicium cathode, graphite cathode, sulfide；
The conductive agent is selected from acetylene black, superconductive carbon black.
The lithium ion battery negative material preparation method of sesbania gum water-based binder, it is characterised in that：
Comprise the following steps：
Step 1：The sesbania gum of formula 1 or sesbania gum derivative are configured to the aqueous solution of 1-3wt%；
Formula 1
Wherein, R- is H or CH2COO-；
Step 2：Active material and conductive agent are placed in mortar and are ground 5-10 minutes；
Step 3：The binding agent prepared in step 1 is added dropwise in the mixture of step 2, both mass ratioes are 1:10-1:5, grind
It is milled to binding agent and is uniformly mixed in active material and conductive agent；
Step 4：Deionized water is added dropwise in the mixture that step 3 is obtained, then is fully ground 20-30 minutes；
Step 5：Step 4 is obtained into mixture to fall on Cu pieces, even spread；
Step 6：The rapid forced air drying of copper sheet that step 5 is obtained obtains pole piece, pole piece vacuum drying to go water removal；
Step 7：The pole piece cut-parts that will be vacuum dried weigh after by assemble battery.
The present invention has advantages below：
From large biological molecule sesbania gum and its derivative as aqueous binders, the binding agent has good water-soluble the present invention
Property, elasticity and adhesive property, while ensure that close electronics contact and form the pole piece structure of stabilization, buffered battery charge and discharge
The expansion and contraction of volume in electric process.This aqueous binders wide material sources, it is with low cost, and green non-pollution.
Sesbania gum system binding agent proposed by the invention is applied to lithium ion battery negative material and prepares electrode slice, and battery is followed
Ring performance is improved, and uses new binding agent wide material sources, is the novel binders of environmental protection with water solubility.In view of
The superperformance of silicium cathode, by the use of water-soluble sesbania gum and its derivative as battery binding agent, to the strategy of sustainable development
Implementing and promote the commercialization process of Si negative poles undoubtedly has important effect.
Brief description of the drawings
Fig. 1 is the cyclicity of the embodiment of the present invention 1 and the silicium cathode of comparative example 2 under the charging and discharging currents density of 100mA/g
Can test curve.
Fig. 2 is the Nyquist of the ac impedance measurement after the embodiment of the present invention 1 and the silicon electrode of comparative example 2 are circulated at 5 times
Figure.
Specific embodiment
With reference to specific embodiment, the present invention will be described in detail.
The initial raw material of sesbania gum system binding agent proposed by the invention is sesbania, and sesbania gum is from annual legume
Extracted in sesbania, therefore wide material sources, it is with low cost, and green non-pollution.The further carboxy methylation of sesbania gum can be made
The derivatives such as standby carboxymethyl sesbania gum.
The present invention is using sesbania gum and its derivative as lithium ion battery negative material binding agent.Sesbania gum is from sesbania
In the natural plant polyose that extracts.Sesbania gum contains the hydroxyl of a large amount of polarity, with good water-soluble, elastic and caking property
Energy.The hydroxyl of the polarity of sesbania gum is beneficial to form hydrogen bond, so as to alleviate bulk effect.On the other hand, sesbania gum ehter bond is lonely right
Electronics can form hapto with lithium ion, and lithium ion can be moved between the hapto of sesbania gum, realize effectively turning for lithium ion
Move.Sesbania gum system binding agent can improve the high rate capability and stable circulation performance of lithium ion battery negative material, extension electricity
Pond service life.
The sesbania gum water-based binder, is the sesbania gum and its derivative shown in formula 1；
Formula 1
Wherein, R- is H or CH2COO-；
Dispersion is deionized water.
Described sesbania gum and its range of viscosities of derivative are 200-1300 mPa.s.
Above-mentioned sesbania gum water-based binder can be used as lithium ion battery negative material binding agent, lithium ion battery negative material
The constituent of material is by mass percentage：
Active material:Conductive agent:Binding agent=（50-80）:（10-30）:（10-20）；
Wherein, binding agent is the sesbania gum and its derivative shown in formula 1, and dispersion is deionized water；
Formula 1
Wherein, R- is H or CH2COO-。
The active material is selected from silicium cathode, graphite cathode, sulfide；
The conductive agent is selected from acetylene black, superconductive carbon black.Binding agent used is generally first configured to 1-3wt%'s in the present invention
Solution, the electrode material for preparing lithium ion battery, slurry is allocated in preparation process using deionized water as diluent
It is dilute thick.The negative material constituent of the lithium ion battery is by mass percentage, active material:Conductive agent:Binding agent=
50-80:10-30:10-20.Lithium ion battery anode active material, including silicium cathode, graphite cathode and sulfide, conductive agent are excellent
Elect acetylene black or superconductive carbon black as.The slurry time is no less than 30 minutes during preparation, and coating thickness is 100-200 μm（It is preferred that
100nm）, it is 60-80 DEG C to dry film temperature.
The lithium ion battery negative material preparation method of sesbania gum water-based binder, comprises the following steps：
Step 1：The sesbania gum of formula 1 or sesbania gum derivative are configured to the aqueous solution of 1-3wt%；
Formula 1
Wherein, R- is H or CH2COO-；
Step 2：Active material and conductive agent are placed in mortar and are ground 5-10 minutes；
Step 3：The binding agent prepared in step 1 is added dropwise in the mixture of step 2, both mass ratioes are 1:10-1:5, grind
It is milled to binding agent and is uniformly mixed in active material and conductive agent；
Step 4：Deionized water is added dropwise in the mixture that step 3 is obtained, then is fully ground 20-30 minutes；
Step 5：Step 4 is obtained into mixture to fall on Cu pieces, even spread；
Step 6：The rapid forced air drying of copper sheet that step 5 is obtained obtains pole piece, pole piece vacuum drying to go water removal；
Step 7：The pole piece cut-parts that will be vacuum dried weigh after by assemble battery.
Embodiment 1
It is first the aqueous solution that 200 mPa.s shitosans are configured to 1 wt% by viscosity.Weigh the second of 70 mg nano Sis and 30.0mg
Acetylene black is placed in mortar, is ground 10 minutes, and the sesbania glue solution of 1 wt% of 0.20g is then added dropwise.Grinding is extremely bonded for 5 minutes
After agent is uniformly mixed in Si powder and carbon dust, 1 mL deionized waters are added dropwise, then be fully ground 15-10 minutes.By the mixing of pasty state
Thing falls on Cu pieces, with 100 μm of scraper even spread, rapidly as in 60 DEG C of air dry oven, is taken out after five minutes.
Then pole piece is put into vacuum drying chamber, 80 DEG C of constant-temperature vacuums dry 6h.After the pole piece cut-parts that will be vacuum dried are weighed, will
Be assembled in glove box in 2032 battery cases, with lithium piece as positive pole, with polyethylene film as barrier film, with 1mol/L LiPF6
EC/DMC/DEC (v/v/v=1/1/1) carries out constant current charge-discharge test for electrolyte assembled battery.
Embodiment 2
From unlike example 1 by the use of the sesbania gum that viscosity is 650 mPa.s as binding agent.
Embodiment 3
From unlike example 1 by the use of the sesbania gum that viscosity is 1300 mPa.s as binding agent.
Embodiment 4
From unlike example 1 by the use of the carboxymethyl sesbania gum that viscosity is 400 mPa.s as binding agent.
Embodiment 5
From unlike example 1 by the use of the carboxymethyl sesbania gum that viscosity is 700 mPa.s as binding agent.
Embodiment 6
It is first the aqueous solution that 650 mPa.s sesbania gums are configured to 3 wt% by viscosity.Weigh the acetylene black of 90mg graphite and 10mg in
In mortar, grind 10 minutes, the 3 wt% sesbania glue solutions of 0.20g are then added dropwise.Grinding uniformly mixes to binding agent for 5 minutes
Afterwards, 1.5mL deionized waters are added dropwise, then are fully ground 15-10 minutes.The mixture of pasty state is fallen on Cu pieces, with 100 μm
Scraper even spread, rapidly as in 70 DEG C of air dry oven, takes out after five minutes.Then pole piece is put into vacuum drying chamber
In, 80 DEG C of constant-temperature vacuums dry 6h.After the pole piece cut-parts that will be vacuum dried are weighed, it is assembled in 2032 electricity in glove box
It is to electrode, with polyethylene film as barrier film, with 1mol/L LiPF with lithium piece in the shell of pond6 EC/DMC/DEC(v/v/v=1/1/1)
For electrolyte assembled battery carries out constant current charge-discharge test.
Embodiment 7
It is first the aqueous solution that 800 mPa.s sesbania gums are configured to 2wt% by viscosity.Weigh 50mg nanometers of SnS2With the acetylene of 20mg
It is black to be ground 10 minutes in mortar, the 2wt% sesbania glue solutions of 0.20g are then added dropwise.Grinding 5 minutes it is uniform to binding agent
After mixing, l.5 mL deionized waters are added dropwise, then be fully ground 15-10 minutes.The mixture of pasty state is fallen on Cu pieces, with 100
μm scraper even spread, rapidly as in 70 DEG C of air dry oven, taken out after five minutes.Then pole piece is put into vacuum to do
In dry case, 80 DEG C of constant-temperature vacuums dry 6h.After the pole piece cut-parts that will be vacuum dried are weighed, it is assembled in glove box
It is to electrode, with polyethylene film as barrier film, with 1mol/L LiPF with lithium piece in 2032 battery cases6 EC/DMC/DEC(v/v/v=
1/1/1) for electrolyte assembled battery carries out constant current charge-discharge test.
Comparative example 1
From, by the use of PVDF as binding agent, adjoin pyrrolidone (NMP) as retarder thinner with N- methyl, accordingly unlike example 1
Baking film temperature be increased to 120 DEG C (vacuum drying).
Comparative example 2
It is the carboxymethylcellulose calcium of 200-1300mPa.s from viscosity is utilized unlike example 1（CMC）As binding agent.
Below by charge and discharge cycles and ac impedance spectroscopy to the negative pole material of sesbania gum system proposed by the present invention binding agent
The chemical property of material is tested and characterized.
1st, cycle performance test
Fig. 1 is that the cycle performance of the embodiment of the present invention 1 and the silicium cathode of comparative example 2 under the charging and discharging currents density of 100mA/g is surveyed
Examination curve.
Table 1 is the cycle performance of the embodiment of the present invention and comparative example silicon electrode under the charging and discharging currents density of 200mA/g
Test.
Table 1 is its corresponding capacity and efficiency for charge-discharge.As it can be seen from table 1 the electric discharge first of carboxymethyl sesbania gum is held
Amount up to 3640 mAh/g, and the theoretical capacity 4200mAh/g of Si is close.PVDF is only as the efficiency first of binding agent
68.3%, and the efficiency first of CMC and shitosan system binding agent is respectively 81% and more than 86%.When circulating for the 200th time, PVDF
The electrode discharge capacity for making binding agent with CMC is below 50 mAh/g.And the discharge capacity of the electrode of sesbania gum system binding agent will
Far better than them.Such as, the sesbania gum of viscosity 200mPa.s is 613 mAh/g, and the sesbania gum of viscosity 650mPa.s is 806
The sesbania gum of mAh/g, viscosity 1300mPa.s is 795 mAh/g, and the carboxymethyl sesbania gum of viscosity 400mPa.s is 823 mAh/g,
The carboxymethyl sesbania gum of viscosity 700mPa.s is 879 mAh/g.Therefore sesbania gum and its derivative binding agent cycle performance keep
Good, discharge capacity is above 500 mAh/g after 200 circulations.
From Table 2, it can be seen that under discharge current density high, compared to PVDF and CMC, sesbania gum proposed by the present invention
It is that electrode prepared by binding agent still shows superior performance.The discharge capacity first of carboxymethyl sesbania gum remains to reach
3286mAh/g, efficiency is 87.8% first.When the 200th circulates, the electrode that PVDF and CMC makees binding agent is respectively 7 Hes
28mAh/g, and the sesbania gum of the mPa.s of viscosity 200 is 569mAh/g, the sesbania gum of viscosity 650mPa.s is 687mAh/g, viscosity
The sesbania gum of 1300mPa.s is 703mAh/g, and the carboxymethyl sesbania gum of viscosity 400mPa.s is 662 mAh/g, viscosity
The carboxymethyl sesbania gum of 700mPa.s is 735mAh/g.Therefore sesbania gum system binding agent shows preferable chemical property.
2nd, ac impedance measurement
Fig. 2 is the Nyquist figures of the ac impedance measurement after the embodiment of the present invention 1 and the silicon electrode of comparative example 2 are circulated at 5 times.It is high
The circular arc in frequency area represents charge transfer resistance, and its diameter shows the size of reaction resistance value.Contrast different binding agents
The high frequency arc radius of Nyquist figures are it can be found that CMC makees the charge transfer resistance maximum after binding agent is circulated at 5 times, carboxylic first
The charge transfer resistance of base sesbania gum binder electrode is minimum.
Present disclosure is not limited to cited by embodiment, and those of ordinary skill in the art are by reading description of the invention
And any equivalent conversion taken technical solution of the present invention, it is claim of the invention and is covered.
Claims (6)
1. sesbania gum water-based binder, it is characterised in that：
Described binding agent is the sesbania gum and its derivative shown in formula 1；
Formula 1
Wherein, R- is H or CH2COO-；
Dispersion is deionized water.
2. sesbania gum water-based binder according to claim 1, it is characterised in that：
Described sesbania gum and its range of viscosities of derivative are 200-1300 mPa.s.
3. sesbania gum water-based binder as claimed in claim 1 as lithium ion battery negative material binding agent application.
4. sesbania gum water-based binder according to claim 3 as lithium ion battery negative material binding agent should
With, it is characterised in that：
The constituent of the lithium ion battery negative material is by mass percentage：
Active material:Conductive agent:Binding agent=（50-80）:（10-30）:（10-20）；
Wherein, binding agent is the sesbania gum and its derivative shown in formula 1, and dispersion is deionized water；
Formula 1
Wherein, R- is H or CH2COO-。
5. sesbania gum water-based binder according to claim 4 as lithium ion battery negative material binding agent should
With, it is characterised in that：
The active material is selected from silicium cathode, graphite cathode, sulfide；
The conductive agent is selected from acetylene black, superconductive carbon black.
6. the lithium ion battery negative material preparation method of sesbania gum water-based binder, it is characterised in that：
Comprise the following steps：
Step 1：The sesbania gum of formula 1 or sesbania gum derivative are configured to the aqueous solution of 1-3wt%；
Formula 1
Wherein, R- is H or CH2COO-；
Step 2：Active material and conductive agent are placed in mortar and are ground 5-10 minutes；
Step 3：The binding agent prepared in step 1 is added dropwise in the mixture of step 2, both mass ratioes are 1:10-1:5, grind
It is milled to binding agent and is uniformly mixed in active material and conductive agent；
Step 4：Deionized water is added dropwise in the mixture that step 3 is obtained, then is fully ground 20-30 minutes；
Step 5：Step 4 is obtained into mixture to fall on Cu pieces, even spread；
Step 6：The rapid forced air drying of copper sheet that step 5 is obtained obtains pole piece, pole piece vacuum drying to go water removal；
Step 7：The pole piece cut-parts that will be vacuum dried weigh after by assemble battery.
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| CN201710214843.5A CN106928882A (en) | 2017-04-01 | 2017-04-01 | Sesbania gum water-based binder and its application in lithium ion battery negative |
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| CN201710214843.5A CN106928882A (en) | 2017-04-01 | 2017-04-01 | Sesbania gum water-based binder and its application in lithium ion battery negative |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108428869A (en) * | 2018-03-13 | 2018-08-21 | 陕西科技大学 | A kind of polymer composite caking agent and its lithium ion battery negative material and preparation method using and based on its preparation |
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| CN102082273A (en) * | 2010-12-24 | 2011-06-01 | 上海中兴派能能源科技有限公司 | Lithium ion battery and electrode material, electrode paste and electrodes of lithium ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108428869A (en) * | 2018-03-13 | 2018-08-21 | 陕西科技大学 | A kind of polymer composite caking agent and its lithium ion battery negative material and preparation method using and based on its preparation |
| CN108428869B (en) * | 2018-03-13 | 2020-09-29 | 陕西科技大学 | Polymer composite adhesive, application thereof, lithium ion battery cathode material prepared based on polymer composite adhesive and preparation method |
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Application publication date: 20170707 |