CN106753044A - A kind of preparation method of lithium ion battery aqueous binders - Google Patents
A kind of preparation method of lithium ion battery aqueous binders Download PDFInfo
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- C09J105/00—Adhesives based on polysaccharides or on their derivatives, not provided for in groups C09J101/00 or C09J103/00
- C09J105/04—Alginic acid; Derivatives thereof
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- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/622—Binders being polymers
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Abstract
A kind of preparation method of lithium ion battery aqueous binders, is related to a kind of energy-storage battery.There is provided that intensity is high, cost is relatively low, environmental protection, a kind of simple preparation method of lithium ion battery aqueous binders of preparation method.Sodium alginate and crosslinking agent are mixed, gel is formed after cross-linking reaction, obtain final product lithium ion battery aqueous binders.Gained lithium ion battery aqueous binders are a kind of lithium ion battery high intensity water-based binders.The hardness of adhesive film is lifted at double, and this advantageously reduces and uses the electrode surface of binding agent involved in the present invention, the rupture event in charge and discharge cycles, so as to lift its cycle performance.
Description
Technical field
The present invention relates to a kind of energy-storage battery, more particularly, to a kind of preparation method of lithium ion battery aqueous binders.
Background technology
Lithium ion battery is because its average output voltage is high, specific energy is high, self discharge is small, memory-less effect the advantages of, such as
The energy storage device of all kinds of portable electric appts is widely used as in modern daily life.In recent years, as consumer is to higher energy
The demand of density lithium ion battery is constantly lifted, and research of the people to the electrode material of height ratio capacity is also increasing year by year.However,
In the research of the electrode material of these height ratio capacities, some challenges, such as negative material of theoretical specific capacity high are often also faced with
Silicon, tin etc., due to, with huge Volume Changes, being easily broken efflorescence in material charge and discharge process, make battery capacity decay, and follow
Ring stability is not good；When then there is first charge-discharge in the lithium-rich manganese-based anode material of height ratio capacity, material structure irreversible transformation,
In charge and discharge process the problems such as voltage continuous decrement, again result in circulating battery and be difficult to keep stabilization.
Binding agent is to maintain one of key factor of electrode structure stabilization.A kind of excellent binding agent can be in holding electrode material
Expect Stability Analysis of Structures, prevent electrode material from departing from collector, maintaining the aspects such as pole piece conductive network to play vital work
With.The binding agent Kynoar commonly used in current commercial Li-ion battery, it is wide because it is relatively stable in the electrolytic solution
It is general to use.However, when this binding agent is on the various new electrode materials for height ratio capacity, effect is then less than satisfactory,
Its subject matter is that binding agent mechanical strength is not enough, it is impossible to effectively maintain the Stability Analysis of Structures of active material；Meanwhile, binding agent
It is weak with active material intermolecular forces, it is difficult to suppress disengaging of the material from electrode surface.In addition, Kynoar (PVDF) only dissolves
In the specific solvents such as 1-METHYLPYRROLIDONE (NMP), this cause electrode fabrication cost increase, and manufacturing process volatilize it is molten
Agent is harmful.
At present, existing multinomial research reports some novel binders, such as carboxymethylcellulose calcium (Chinese patent
CN100457848), sodium alginate and shitosan (A of Chinese patent CN 102760883), guar gum (Chinese patent CN
104934609 A), Lithium polyacrylate etc., they are higher due to mechanical strength, can effectively inhibitory activity material in battery charging and discharging
During structure destruction；Their adhesions to active material are also relatively strong simultaneously, make active material be more difficult to depart from collector；
And these binding agents are water solubility, electrode production cost can be made to reduce and safer.These advantages compare them
Kynoar, the binding agent for being more suitable for the new type lithium ion battery of high-energy-density is used.Wherein, sodium alginate is bonded
Compared to cross-linked chitosan, guar gum etc., its mechanical strength is more lower slightly, the volume in buffers active material charge and discharge process for agent
The aspect such as change or suppression structure transformation shows slightly not enough.By adding polyvalent metal ion such as Al3+、Ba2+Deng the mode of crosslinking
Its mechanical strength can be strengthened, using by obtained with upper type it is cross-linking modified after binding agent, may be such that battery positive and negative electrode
Cyclical stability of the material in loop test is obviously improved.
The content of the invention
It is an object of the invention to provide intensity it is high, cost is relatively low, environmental protection, a kind of simple lithium ion of preparation method
The preparation method of battery aqueous binders.
It is of the invention to comprise the following steps that：
Sodium alginate and crosslinking agent are mixed, gel is formed after cross-linking reaction, obtain final product the aqueous bonding of lithium ion battery
Agent.
Gained lithium ion battery aqueous binders are a kind of lithium ion battery high intensity water-based binders.
The sodium alginate can be 0.01~0.03 with the mass ratio of crosslinking agent.The sodium alginate can use quality percentage
Concentration is 1.5%, and solution viscosity is the sodium alginate of 900~1300mPa s；The crosslinking agent can be using the water of multivalent metal salt
Solution, the molar concentration of metal ion can be 1~5mmol L in the aqueous solution-1, the slaine can use barium salt or aluminium salt,
The barium salt may be selected from barium chloride etc., and the aluminium salt may be selected from the one kind in aluminum sulfate, aluminium chloride etc.；The speed of the stirring can
It is 80~200rpm；The time of the cross-linking reaction can be 0.5~3h.Mixed process can be carried out at normal temperatures, its duration
Different depending on crosslinking agent and cross-linking reaction proportioning, to be mixed is in homogeneous, pellucidity to gel, then cross-linking reaction is completed, you can obtained
Obtain lithium ion battery high intensity water-based binder.
The present invention carries out mechanical performance sign to the lithium ion battery aqueous binders for obtaining, and detailed process is as follows：
The present invention is using the NDJ-5S types rotation viscometer of Shanghai Changji geological instrument Co., Ltd of company production to bonding
Agent viscosity is characterized.Experimentation is as follows：In prepared binding agent, sodium alginate is 0.015 with the mass ratio of crosslinking agent,
Slaine is prepared respectively from barium chloride with aluminum sulfate in crosslinking agent, and concentration of metal ions is 1.8mmol L-1, in stirring best friend
After the completion of connection reaction, gained binding agent is used for viscosity test, test temperature is 20 DEG C.Gained binding agent is according to addition crosslinking agent
Difference, gained barium-alginic acid hydrogel binding agent is designated as Ba-alginate, aluminium-alginic acid hydrogel binding agent is designated as
Al-alginate。
Result shows that under the same conditions, the 1.5wt% sodium alginate gels viscosity without crosslinking agent is 1140mPa
S, and Al-alginate viscosity is 1630mPa s, Ba-alginate viscosity is 30000mPa s, compared to carrying before modified
Rise, the viscosity lifting of wherein Ba-alginate is very huge, and this may be larger with barium ions radius relevant.
Lithium ion battery aqueous binders of the invention are prepared from by sodium alginate with crosslinking agent.The present invention can use upper
The THVS-1M-AD type digital display sample stages Vickers hardness control of Hai Naibo detection techniques Co., Ltd production is with measuring system to viscous
The Vickers hardness for tying agent film is characterized.Experimentation is as follows：The adhesive coated that will be prepared is in smooth glass plate
On, 55 DEG C of drying 10h make binding agent form film in glass pane surface in air dry oven, retell glass plate and are transferred to vacuum
80 DEG C of vacuum drying 10h make its thorough drying in drying box.Gained film is that can be used to Vickers hardness scale levy after drying.Vickers
Hardness test condition is test force 25gf, retention time 15s.
Above-mentioned experimentation is matched somebody with somebody in prepared binding agent, and sodium alginate is 0.02 with crosslinking agent quality ratio, gold in crosslinking agent
Category salt selects barium chloride and aluminum sulfate respectively, and concentration of metal ions is 1.8mmol L-1, testing obtained film thickness need to be more than
0.1mm。
Result shows that under the same conditions, the Vickers hardness of the pure sodium alginate film of unmodified crosslinking is 14.3HV, and
The Vickers hardness of barium-alginate films is 32.0HV, and the Vickers hardness of aluminium-alginate films is 35.0HV, compared to modified
Before, the hardness of adhesive film is lifted at double, and this is advantageously reduced using the electrode surface of binding agent involved in the present invention,
Rupture event in charge and discharge cycles, so as to lift its cycle performance.
Brief description of the drawings
Fig. 1 is the embodiment of the present invention and comparative example silicium cathode in 420mA g-1Cycle performance test under current density is bent
Line.In Fig. 1, abscissa is period Cycle Number, and left ordinate is Capacity (mAh/g-1), right ordinate is
Effciency (%)；Mark is embodiment 1, and zero is embodiment 2, ● it is comparative example 1.
Fig. 2 is the embodiment of the present invention and comparative example silicium cathode in 2100mA g-1Cycle performance test under current density is bent
Line.In fig. 2, abscissa is period Cycle Number, and left ordinate is Capacity (mAh/g-1), right ordinate is
Effciency (%)；Mark is embodiment 1, and zero is embodiment 2, ● it is embodiment 3.
Fig. 3 is the embodiment of the present invention and comparative example lithium-rich manganese-based anode in 100mAg-1Current density under loop test
Curve.In figure 3, abscissa is period Cycle Number, and ordinate is Capacity (mAh/g-1)；Mark is implementation
Example 3, zero is embodiment 4, and △ is comparative example 2, ● it is comparative example 3.
Fig. 4 is the embodiment of the present invention and comparative example lithium-rich manganese-based anode in 100mAg-1Current density under in cyclic process
Electric discharge in press change curve.In fig. 4, abscissa is period Cycle Number, and ordinate is Average
cischargevoltage(V)；Mark is embodiment 3, and zero is embodiment 4, and △ is comparative example 2, ● it is comparative example 3.
Fig. 5 is the SEM figures before comparative example electrode charge and discharge circulation of the present invention.
Fig. 6 and Fig. 7 are the SEM figures before two embodiment electrode charge and discharges circulations in the present invention.
Fig. 8 is the SEM figures after comparative example electrode charge and discharge circulation of the present invention.
Fig. 9 and Figure 10 are the SEM figures after two embodiment electrode charge and discharges circulations in the present invention.
In Fig. 5~10, scale is 20 μm.
Specific embodiment
Embodiment 1
Aluminum sulfate is configured to aluminium ion concentration 1.8mmol L-1The aqueous solution as crosslinking agent.Weigh sodium alginate
0.02g is stirred in measuring cup with 1mL crosslinking agents and mixed, to forming homogeneous, transparent gel.Weigh nano-silicon 0.06g and second
Acetylene black 0.02g, ground and mixed is then transferred to be mixed with gained gel stirring before this in measuring cup to uniform in mortar
Close, persistently stir 6~12h, be homogenized to being formed.15 μm of Copper Foil of thickness is cut into the copper sheet of diameter 12mm, 10wt% salt is used
Acid, deionized water, acetone wash normal-temperature vacuum drying successively.Weigh afterwards and record each copper sheet quality.By the uniform painting of gained homogenate
Cloth is vacuum dried 10h under the conditions of 80 DEG C afterwards on above-mentioned copper sheet.Gained pole piece weighing after drying, and it is transferred to gloves
It is used for assembled battery in case.Assembled battery uses 2025 type battery cases, battery diaphragm to use the types of Celgard 2400, and electrolyte is
1molL-1LiPF6EC/DMC/DEC (︰ 1 of 1 ︰ 1)+2wt%VC+10wt%FEC solution.After battery is completed, stand 10h with
On, then carry out constant current with the 2001 type testers of Wuhan Land Electronic Co., Ltd. under the conditions of 30 DEG C of constant temperature and fill
Discharge test, it is 0.01~1.2V that test voltage is interval.
Embodiment 2
Barium chloride is configured to barium ions concentration 1.8mmol L as different from Example 1-1The aqueous solution as crosslinking
Agent.
Embodiment 3
Barium chloride is configured to barium ions concentration 1.8mmol L-1The aqueous solution as crosslinking agent.Weigh sodium alginate
0.02g is stirred in measuring cup with 1mL crosslinking agents and mixed, to forming homogeneous, transparent gel.Weigh lithium-rich manganese-based anode material
Li1.16Mn0.6Ni0.12Co0.12O2The 0.16g and 0.02g of BP 2000, then ground and mixed is shifted to uniform in mortar
Mix with gained gel stirring before this into measuring cup, persistently stir 6~12h, be homogenized to being formed.20 μm of aluminium foil of thickness is cut
The aluminium flake of diameter 12mm is segmented into, is dried after being washed successively with 10wt% oxalic acid solutions, deionized water, acetone.Record is weighed afterwards
Each aluminium flake quality.Gained homogenate is uniformly coated on above-mentioned aluminium flake, 10h is vacuum dried under the conditions of 100 DEG C afterwards.By drying
Gained pole piece weighing afterwards, and be transferred in glove box for assembled battery.Assembled battery uses 2025 type battery cases, battery diaphragm
Using the types of Celgard 2400, electrolyte is 1mol L-1LiPF6EC/DMC (1 ︰ 1) solution.After battery is completed, stand
More than 10h, then carries out perseverance under the conditions of 30 DEG C of constant temperature with the 2001 type testers of Wuhan Land Electronic Co., Ltd.
Current charge-discharge electrical testing, it is 2.0~4.8V that test voltage is interval.
Embodiment 4
Aluminum sulfate is configured to aluminium ion concentration 1.8mmol L as different from Example 3-1The aqueous solution as crosslinking
Agent.
Comparative example 1
The cross-linker moiety of addition is replaced with the deionized water of equivalent as different from Example 1.
Comparative example 2
The binding agent partial replacement that will be added as different from Example 3 is addition 10wt%PVDF 0.2g and 0.65mL
NMP。
Comparative example 3
Cross-linker moiety is replaced with addition 1mL deionized waters as different from Example 3.
Below by SEM before and after the positive pole using different binding agents, the circulation of cathode pole piece constant current charge-discharge, electrode charge and discharge
Figure becomes to appearance structure before and after the chemical property of the electrode using high intensity modified binder proposed by the present invention and discharge and recharge
Change is tested and characterized.
1. cycle performance test
Fig. 1 is the embodiment of the present invention 1,1 nanometer of silicon electrode of embodiment 2 and comparative example in 420mA g-1Following under current density
Ring performance test curve.It is obvious that the initial charge ratio of the electrode (embodiment 1) with Al-alginate as binding agent
Capacity is 3462mAh g-1, it is closer to the theoretical charge specific capacity 3570mAh g of silicon-1, in its stable circulation 335 weeks, its
Capability retention is 58.5%, and flex point occurs in its cyclic curve afterwards, and capacity attenuation is accelerated.And with Ba-alginate be bond
The electrode (embodiment 2) of agent, its initial charge specific capacity 3562mAh g-1, the theoretical charge specific capacity of silicon is equally closer to,
In its stable circulation 320 weeks, its capability retention 53.4% was that flex point occurs in its cyclic curve afterwards, and capacity attenuation is accelerated.
By contrast, with sodium alginate as binding agent electrode (comparative example 1), its initial charge capacity is only 3103mAh g-1, it is remote low
In the use of Ba-alginate or Al-alginate being the electrode of binding agent, when circulating 183 weeks, its specific capacity compares embodiment
1st, the low about 580mAh g of embodiment 2-1, just occurring cyclic curve flex point afterwards, capacity is decayed rapidly.
Fig. 2 is the embodiment of the present invention and comparative example nano-silicon electrode material in 2100mA g-1Cyclicity under current density
Can test curve.Electrode (embodiment 2) with Ba-alginate as binding agent still has 1643mAh g after being circulated through 500 times-1
Specific capacity, its capability retention be 55.4%.Electrode (embodiment 1) with Al-alginate as binding agent is through 500 circulations
1772mAh g are then maintained afterwards-1Specific capacity, its capability retention be 55.6%.By comparison, with sodium alginate as binding agent
Electrode (comparative example 1) through 500 times circulate after only maintain 1019mAh g-1Specific capacity, its capability retention be 33.9%.
Fig. 3 is the embodiment of the present invention 3, embodiment 4 and comparative example 2, the lithium-rich manganese-based anode material of comparative example 3 in 100mA g-1
Current density under loop test curve.It can be seen that electrode (embodiment 3) second week with Ba-alginate as binding agent
Discharge capacity be 234.6mAh g-1, the discharge capacity of electrode (embodiment 4) second week with Al-alginate as binding agent
It is 237.6mAh g-1, 195.3mAh g are respectively by its capacity after 150 circle circulations-1With 181.6mAh g-1, capability retention
Respectively 83.3% and 76.5%.And using PVDF as the electrode (comparative example 2) of binding agent and using sodium alginate as binding agent
Electrode (comparative example 3), the specific discharge capacity of its second week is respectively 217.7mAh g-1With 228.6mAh g-1, by 150 weeks
After circulation, its specific discharge capacity is respectively 66.4mAh g-1With 142.8mAh g-1, capability retention is only 30.5% He
62.5%.It can be seen that compared to sodium alginate, especially compared to being commercialized for binding agent PVDF at present, using Ba-
Alginate and Al-alginate can increase substantially the cyclical stability of material as binding agent, slow down the capacity of material
Decay.
Fig. 4 is the embodiment of the present invention 3, embodiment 4 and comparative example 2, the lithium-rich manganese-based anode material of comparative example 3 in 100mA g-1
Current density under electric discharge in press figure.This it appears that using PVDF as the electrode (comparative example 2) of binding agent, its process
The voltage attenuation of 150 weeks is 0.7029V, using sodium alginate as the electrode (comparative example 3) of binding agent, voltage after circulation in 150 weeks
0.6087V is decayed to, the obvious voltage attenuation that both of which shows, the structure of this explanation material occurs in cyclic process
Obvious change, material structure is unstable.And electrode (embodiment 3) with Ba-alginate as binding agent and with Al-
Alginate is the electrode (embodiment 4) of binding agent, and after circulation in its 150 weeks, voltage attenuation is respectively 0.3615V and 0.2078V,
Contrast and commercialized PVDF and sodium alginate, Ba-alginate and Al-alginate can be obviously as binding agent
Suppress voltage attenuation phenomenon of the material in cyclic process, this shows that the binding agent can be good at the stabilization of protection materials structure
Property, reduce the side reaction between electrolyte and material, so as to slow down the voltage attenuation of material.
Above loop test result shows, using high-strength adhesive proposed by the present invention, can make positive and negative electrode material
Cycle performance is significantly improved.
2.SEM is characterized
The silicium cathode pole piece that Fig. 5~7 are respectively comparative example of the present invention 1, embodiment 1 and embodiment 2 is not carrying out discharge and recharge
SEM figures before test.Each electrode surface is presented uniform fine particle tiling pattern, illustrates that the various homogenate prepared before this exist
Coat very uniform on electrode slice, this be conducive to after test to electrode electro Chemical performance.
The silicium cathode pole piece of Fig. 8~10 respectively comparative example 1, embodiment 1 and embodiment 2 is in 2100mA g-1Current density
The lower pole piece pattern repeated after discharge and recharge 500 times.It can be seen that in Fig. 8 the pole piece of comparative example 1 occur in that it is many obvious
Rupture, and the pole piece of embodiment 1 and embodiment 2 pattern after discharge and recharge then keeps more intact in Fig. 9 and 10, this shows to use
High-strength adhesive proposed by the present invention, has effectively buffered the situation of electrode surface structure destruction in discharge and recharge.
Claims (10)
1. a kind of preparation method of lithium ion battery aqueous binders, it is characterised in that comprise the following steps that：By sodium alginate with
Crosslinking agent is mixed, and gel is formed after cross-linking reaction, obtains final product lithium ion battery aqueous binders.
2. a kind of preparation method of lithium ion battery aqueous binders as claimed in claim 1, it is characterised in that the marine alga
Sour sodium is 0.01~0.03 with the mass ratio of crosslinking agent.
3. a kind of preparation method of lithium ion battery aqueous binders as claimed in claim 1, it is characterised in that the marine alga
Sour sodium is that mass percentage concentration is 1.5%, and solution viscosity is 900~1300mPas.
4. a kind of preparation method of lithium ion battery aqueous binders as claimed in claim 1, it is characterised in that the crosslinking
Agent is the aqueous solution of multivalent metal salt.
5. a kind of preparation method of lithium ion battery aqueous binders as claimed in claim 4, it is characterised in that described water-soluble
The molar concentration of metal ion is 1~5mmol L in liquid-1。
6. a kind of preparation method of lithium ion battery aqueous binders as claimed in claim 4, it is characterised in that the metal
Salt is barium salt or aluminium salt.
7. a kind of preparation method of lithium ion battery aqueous binders as claimed in claim 6, it is characterised in that the barium salt
It is barium chloride.
8. a kind of preparation method of lithium ion battery aqueous binders as claimed in claim 6, it is characterised in that the aluminium salt
Selected from the one kind in aluminum sulfate, aluminium chloride.
9. a kind of preparation method of lithium ion battery aqueous binders as claimed in claim 1, it is characterised in that the stirring
Speed be 80~200rpm.
10. a kind of preparation method of lithium ion battery aqueous binders as claimed in claim 1, it is characterised in that the crosslinking
The time of reaction is 0.5~3h.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109065886A (en) * | 2018-06-27 | 2018-12-21 | 东华大学 | A kind of aqueous mineral binder and its preparation method and application for lithium ion battery silicium cathode |
| CN110048174A (en) * | 2019-04-29 | 2019-07-23 | 中南大学 | A kind of gel batteries dielectric film and its preparation method and application |
| CN113823796A (en) * | 2021-09-09 | 2021-12-21 | 电子科技大学 | Water-based binder based on alginic acid-Prussian blue and preparation method thereof |
| US20220181629A1 (en) * | 2020-12-04 | 2022-06-09 | GM Global Technology Operations LLC | Elastic binding polymers for electrochemical cells |
| CN114614003A (en) * | 2021-12-30 | 2022-06-10 | 嘉兴学院 | Adhesive with double-crosslinked-network structure and preparation method and application thereof |
| CN116565209A (en) * | 2023-07-07 | 2023-08-08 | 深圳海辰储能控制技术有限公司 | Pole piece, preparation method thereof, battery and power utilization device |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109065886A (en) * | 2018-06-27 | 2018-12-21 | 东华大学 | A kind of aqueous mineral binder and its preparation method and application for lithium ion battery silicium cathode |
| CN110048174A (en) * | 2019-04-29 | 2019-07-23 | 中南大学 | A kind of gel batteries dielectric film and its preparation method and application |
| US20220181629A1 (en) * | 2020-12-04 | 2022-06-09 | GM Global Technology Operations LLC | Elastic binding polymers for electrochemical cells |
| CN113823796A (en) * | 2021-09-09 | 2021-12-21 | 电子科技大学 | Water-based binder based on alginic acid-Prussian blue and preparation method thereof |
| CN113823796B (en) * | 2021-09-09 | 2022-12-27 | 电子科技大学 | Water-based binder based on alginic acid-Prussian blue and preparation method thereof |
| CN114614003A (en) * | 2021-12-30 | 2022-06-10 | 嘉兴学院 | Adhesive with double-crosslinked-network structure and preparation method and application thereof |
| CN116565209A (en) * | 2023-07-07 | 2023-08-08 | 深圳海辰储能控制技术有限公司 | Pole piece, preparation method thereof, battery and power utilization device |
| CN116565209B (en) * | 2023-07-07 | 2023-10-13 | 深圳海辰储能控制技术有限公司 | Pole piece, preparation method thereof, battery and power utilization device |
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| CN106753044B (en) | 2019-01-22 |
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