CN109950619A - A kind of high pressure ternary lithium battery gel polymer electrolyte and preparation method thereof - Google Patents
A kind of high pressure ternary lithium battery gel polymer electrolyte and preparation method thereof Download PDFInfo
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- CN109950619A CN109950619A CN201910295108.0A CN201910295108A CN109950619A CN 109950619 A CN109950619 A CN 109950619A CN 201910295108 A CN201910295108 A CN 201910295108A CN 109950619 A CN109950619 A CN 109950619A
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Abstract
The invention discloses a kind of high pressure ternary lithium battery gel polymer electrolytes, are mainly prepared by following several raw materials: copolymer powder, organic solvent and inorganic additive.Electrolyte provided by the invention can reduce positive electrode surface-active and inhibit electrode material and electrolyte that side reaction occurs, the adsorbable micro-moisture of inorganic salts and with hydrogen fluoride reaction micro in battery, reduce the moisture and acidity in electrolyte, and then battery charging voltage is improved, improve the cycle performance and security performance of electrolyte.In addition, the invention also discloses the electrolyte preparation method, the preparation method is easy to operate, preparation is convenient, it is suitable for mass industrialized production.
Description
Technical field
The present invention relates to lithium-ion battery electrolytes preparation technical fields, and in particular to a kind of high voltage ternary lithium battery is solidifying
Xanthan polymer electrolyte and preparation method thereof.
Background technique
Since lithium ion battery in 1990 enters miniature electric energy storage field, research and reality in more than 20 years have passed through
It tramples, has come into the fast-developing stage.With the continuous expansion in lithium ion battery market, traditional lithium ion battery is opposite
The unstable and safety of lower specific energy, structure, is difficult meet the needs of market.Therefore, exploitation have high-energy-density,
The lithium ion battery of high safety has become the main target of researchers struggle.
The performance of lithium ion battery and selection, preparation process and the performance of electrode material for battery etc. are closely related.With Li
[Ni0.5Co0.2Mn0.3]O2For representative stratiform Li-Ni-Co-Mn-O series ternary material have both lithium nickelate, cobalt acid lithium,
The advantages of LiMn2O4, and its respective deficiency is compensated for a certain extent.In practical applications, as people are to battery high energy
The requirement of metric density, the operating voltage for improving electrode material become a kind of important means, but under the conditions of high working voltage, ternary
The charging and discharging capacity of material will appear attenuation trend, show poor cycle performance and high rate performance.Cause this phenomenon
The reason of, on the one hand it is that polarization phenomena and transition metal dissolution easily occur for ternary material under high working voltage, leads to material
Structural damage makes material electrochemical performance be deteriorated;On the other hand, high voltage will lead to electrolyte oxygenolysis and its with work
The generation of side reaction, causes the corrosion of active material between property material.Therefore, these problems are faced, study ternary material in height
Chemical property under voltage, and electrode performance is improved by modified method and is had a very important significance.
Application publication number is CN1047601571A, and data of publication of application is that the patent of invention of 2015.06.10 discloses one kind
High-voltage electrolyte and lithium ion battery containing the electrolyte.The high-voltage electrolyte is that 0 .1% is added in general electrolytic liquid
The functional additive of~5% mass percent, the functional additive refer to two nitrile compounds of alkene.The invention uses nitrogenous
The high pressure film for additive of element and two nitrile compounds of the alkene of double bond functional group as lithium-ion electrolyte, such additive base
In the oxidation or reduction of double bond, one layer of fine and close passivation can be formed in anode and negative terminal surface during first charge-discharge
Film.The introducing of stable cyano so that skin covering of the surface electrochemistry with it is chemically more stable.Lithium containing this electrolysis additive
Cycle performance of the ion battery at 3~4 .5V is improved, and lithium ion battery safety performance, service life and energy are improved
Metric density.
Application publication number is CN107195970A, and data of publication of application discloses a kind of exist for the patent of invention of 2017.09.22
In general electrolytic liquid add quality 1%-5% benzal fluoride sulfone high-pressure type electrolyte, benzal fluoride sulfone can be used as lithium from
The high pressure film for additive of sub- electrolyte, since the additive has lower oxidizing potential, energy during first charge-discharge
It is enough to form one layer of form compact and stable interfacial film in positive electrode surface, optimize positive electrode surface film, it is suppressed that the surface-active of electrode, from
And inhibit electrolyte and electrode active material further contact and the formation of HF, less electrolyte bulk solvent is in electrode
The oxygenolysis on surface.
Application publication number is CN102244291 A, and data of publication of application is that the patent of invention of 2011.11.16 discloses one kind
Gel polymer lithium ion battery electrolyte and preparation method thereof.The electrolyte is Kynoar system gel electrolyte,
In be added with modified glass-fiber.After being blended by the modified glass-fiber for crossing PVDF-HFP and ball milling, it is excellent to obtain performance
The polymer film of self-supporting more.Since modified glass-fiber has a certain amount of nano particle, in addition glass fibre building has by force
The supporting network of power so that the polymer has the microcellular structure of fabulous crosslinking, splendid absorbent, and has stronger
Mechanical strength, but the shortcomings that invention is that conductivity is lower.
The main product of lithium ion battery electrolyte materials or liquid organic electrolyte material currently on the market, but have
The problems such as machine liquid electrolyte is inflammable, and the lithium ion battery for adding liquid electrolyte is easy to happen leakage and flatulence is to hold
Easily cause explosion, results in a series of safety problems.The application of polymer dielectric makes lithium ion battery have higher safety
Property and energy density, so that battery with flexible design, can be avoided the electrolyte leakage problem of battery, but gel polymer is electrolysed
Conductivity is lower at room temperature for matter, makes using being restricted.
Summary of the invention
In view of the above-mentioned problems, the object of the present invention is to provide a kind of high pressure ternary lithium battery gel polymer electrolytes, it can
It reduces positive electrode surface-active and inhibits electrode material and electrolyte that side reaction occurs, reduce the moisture and acidity of electrolyte,
The cycle performance and security performance for improving electrolyte, the present invention also provides the preparation method of the electrolyte, the preparation methods
Operating process is simple, and preparation is convenient.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of high pressure ternary lithium battery gel polymer electrolyte, is mainly prepared by following several raw materials: copolymer powder,
Organic solvent and inorganic additive.
The copolymer powder is Kynoar-hexafluoropropene powder.
Preferably, the inorganic additive is in lithium carbonate, aluminium oxide, silica, magnesia, zinc oxide or titanium dioxide
A combination of one or more.
Further, the inorganic additive is partial size < 150nm particle.
Preferably, the organic solvent be one of acetone, N-N dimethylformamide, N- methyl pyrrolidone or
A variety of compositions.
A kind of high pressure ternary lithium battery method for preparing gel polymer electrolyte, including the following steps:
1) copolymer powder of certain mass is dissolved in organic solvent, inorganic additive is then added, in 60-70 DEG C of temperature
It is uniformly mixed within lower heating stirring 8-10 hours, obtains coating liquid;
2) coating liquid is cast on the glass plate of smooth pieces, after coating liquid is struck off, is placed in 20-80 DEG C together with glass plate
It is separated after carrying out within 50-70 minutes in water, then is transferred in 25-60 DEG C of water and handles 8-12 hours, it is solidifying that lithium ion battery is obtained after drying
Xanthan polymer film;
3) lithium ion battery gel polymer film after -90 ° of vacuum drying 20-30 hours, is impregnated into 1-3 in the electrolytic solution at 80 °
Hour to get arrive required lithium ion battery gel polymer electrolyte.
It is 0.5-5% that added inorganic additive, which accounts for the mass percent of obtained coating liquid, in the step 1).
It is 5%- that added copolymer powder, which accounts for the mass percent of obtained coating liquid quality, in the step 1)
15%。
Preferably, the molar concentration of the electrolyte in the step 3) is the .0mol/L of 1 .0~4.
Preferably, the electrolyte in the step 3) be LiClO4/EC-DMC solution, LiClO4/EC-PC solution,
At least one of LiClO4/EC-DEC solution.
Compared with prior art, the present invention Kynoar-hexafluoropropene base in the present invention after mineral-modified is solidifying
Xanthan polymer electrolyte, not only improves the mechanical performance of polymer, and increases the porosity of polymer film, leads to Li+
Ion mobility is accelerated, and ionic conductivity is improved.Electrolyte provided by the invention can reduce positive electrode surface-active and
Inhibit electrode material and electrolyte to occur side reaction, the adsorbable micro-moisture of inorganic salts and with hydrogen fluoride reaction micro in battery,
The moisture and acidity in electrolyte are reduced, and then improves battery charging voltage, improves the cycle performance and security performance of electrolyte.
In addition, the preparation method of electrolyte of the invention is easy to operate, preparation is convenient, it is suitable for mass industrialized production.
Specific embodiment
To more fully understand those skilled in the art to the present invention, the present invention is done With reference to embodiment
It further illustrates, but the embodiment is not intended as restriction of the invention.
Unless otherwise instructed, the content in embodiment is mass percentage to following embodiment.
Embodiment 1
(1) lithium carbonate nano for being 0.5% by mass percent, Kynoar-hexafluoropropene that mass percent is 5%
Copolymer powder is dissolved in n,N-Dimethylformamide, 60 DEG C at a temperature of heating stirring 8 hours be uniformly mixed, obtain film
Liquid;(2) it by the glass plate of coating liquid casting smooth pieces, after coating liquid is struck off, is placed in together with glass plate in 60 DEG C of water
It is separated after carrying out within 60 minutes, then is transferred in 60 DEG C of water and handles 10 hours.At lithium ion battery gel polymer film after drying;
(3) lithium ion battery gel polymer film is immersed in 3 in LiClO4/EC-DEC electrolyte after 80 ° are dried in vacuo 24 hours
Hour, and the concentration of LiClO4 is 4 mol/L, finally obtains the lithium ion battery gel polymer electrolyte.
Embodiment 2:
(1) lithium carbonate nano for being 5% by mass percent, Kynoar-hexafluoropropene that mass percent is 15%
Copolymer powder is dissolved in N-Methyl pyrrolidone, 60 DEG C at a temperature of heating stirring 8 hours be uniformly mixed, obtain film
Liquid;(2) it by the glass plate of coating liquid casting smooth pieces, after coating liquid is struck off, is placed in together with glass plate in 60 DEG C of water
It is separated after carrying out within 60 minutes, then is transferred in 60 DEG C of water and handles 10 hours.At lithium ion battery gel polymer film after drying;
(3) lithium ion battery gel polymer film is immersed in 3 in LiClO4/EC-DEC electrolyte after 80 ° are dried in vacuo 24 hours
Hour, and the concentration of LiClO4 is 4 mol/L, finally obtains the lithium ion battery gel polymer electrolyte.
Embodiment 3:
(1) silica nano particle for being 0.5% by mass percent, Kynoar-hexafluoropropene that mass percent is 5%
Copolymer powder is dissolved in n,N-Dimethylformamide, 60 DEG C at a temperature of heating stirring 8 hours be uniformly mixed, obtain film
Liquid;(2) it by the glass plate of coating liquid casting smooth pieces, after coating liquid is struck off, is placed in together with glass plate in 25 DEG C of water
It is separated after carrying out within 70 minutes, then is transferred in 25 DEG C of water and handles 12 hours.At lithium ion battery gel polymer film after drying;
(3) lithium ion battery gel polymer film is immersed in 3 in LiClO4/EC-PC electrolyte after 80 ° are dried in vacuo 20 hours
Hour, and the concentration of LiClO4 is 2 mol/L, finally obtains the lithium ion battery gel polymer electrolyte.
Embodiment 4:
(1) silica nano particle for being 0.5% by mass percent, Kynoar-hexafluoropropene that mass percent is 5%
Copolymer powder is dissolved in acetone, 70 DEG C at a temperature of heating stirring 8 hours be uniformly mixed, obtain coating liquid;(2) by film
Liquid is poured on the glass plate of smooth pieces, after coating liquid is struck off, is placed in together with glass plate 65 minutes in 25 DEG C of water after carrying out
Separation, then be transferred in 25 DEG C of water and handle 10 hours.At lithium ion battery gel polymer film after drying;(3) by lithium-ion electric
Pond gelatin polymer film is immersed in LiClO4/EC-DEC electrolyte 1.5 hours after 80 ° are dried in vacuo 30 hours, and
The concentration of LiClO4 is 1 mol/L, finally obtains the lithium ion battery gel polymer electrolyte.
Embodiment 5:
(1) titania nanoparticles for being 2.5% by mass percent, Kynoar-hexafluoro that mass percent is 10%
Propylene copolymer powder is dissolved in n,N-Dimethylformamide, 60 DEG C at a temperature of heating stirring 10 hours be uniformly mixed, obtain
To coating liquid;(2) by the glass plate of coating liquid casting smooth pieces, after coating liquid is struck off, 80 DEG C are placed in together with glass plate
Water in carry out within 50 minutes after separate, then be transferred in 60 DEG C of water and handle 8 hours.At lithium ion battery gel polymer after drying
Film;(3) lithium ion battery gel polymer film is immersed in LiClO4/EC-DEC electrolyte after the drying in 20 hours of 90 ° of vacuum
In 1 hour, and the concentration of LiClO4 is 2 mol/L, finally obtains the lithium ion battery gel polymer electrolyte.
Embodiment 6:
(1) aluminum oxide nanoparticle for being 5% by mass percent, Kynoar-hexafluoropropene that mass percent is 10%
Copolymer powder is dissolved in N-Methyl pyrrolidone, 60 DEG C at a temperature of heating stirring 8 hours be uniformly mixed, obtain film
Liquid;(2) it by the glass plate of coating liquid casting smooth pieces, after coating liquid is struck off, is placed in together with glass plate in 60 DEG C of water
It is separated after carrying out within 60 minutes, then is transferred in 60 DEG C of water and handles 10 hours.At lithium ion battery gel polymer film after drying;
(3) lithium ion battery gel polymer film is immersed in 3 in LiClO4/EC-PC electrolyte after the drying in 24 hours of 80 ° of vacuum
Hour, and the concentration of LiClO4 is 2 mol/L, finally obtains the lithium ion battery gel polymer electrolyte.
Comparative example:
(1) Kynoar-hexafluoropropylene copolymer powder that mass percent is 5% is dissolved in n,N-Dimethylformamide,
60 DEG C at a temperature of heating stirring 8 hours be uniformly mixed, obtain coating liquid;(2) by the glass of coating liquid casting smooth pieces
On plate, after coating liquid is struck off, it is placed in 60 minutes in 60 DEG C of water after carrying out and separates together with glass plate, then be transferred in 60 DEG C of water
Processing 10 hours.At lithium ion battery gel polymer film after drying;(3) lithium ion battery gel polymer film is true at 80 °
It after empty drying in 24 hours, is immersed in LiClO4/EC-DEC electrolyte 3 hours, and the concentration of LiClO4 is 4 mol/L, finally
Obtain the lithium ion battery gel polymer electrolyte.
Performance test:
Prepare gel electrolyte membrane:
The Kynoar of composite silicon nitride prepared by embodiment 1-hexafluoropropene base gel polymer electrolyte is cast in mould
In tool, the dry 1h at 50 DEG C, then the dry 48h in 50 DEG C of vacuum ovens, obtains the gel electrolyte with a thickness of 0.7mm
Film.
Conductivity:
Using stainless steel substrates as blocking electrode, simulated battery is prepared, does ac impedance measurement.AC impedance curve is in high frequency region and cross
The intersection value of axis is the ontology impedance of the gel electrolyte membrane.
According to the relationship between the ontology impedance (Rb) and its conductivity (σ): σ=d/ (S*Rb)
The conductivity (σ) of the gel electrolyte membrane can be calculated, wherein d is the thickness of the gel electrolyte membrane, S is institute
State the contact area of gel electrolyte membrane Yu the stainless steel blocking electrode.
Processing machinery performance test sample:
Tensile strength and elongation at break: specimen shape and size are according to the regulation system for meeting GB/T1040 .3-2006.
Tearing strength: specimen shape and size make according to square sample as defined in GB/T 529 is met.
Tensile strength and elongation at break: it is tested according to 1040 .3-2006 of GB/T.
Tearing strength: it is tested according to GB/T 529.
Properties test, acquired property are carried out to gel electrolyte made from the embodiment of the present invention 1~6 and comparative example 1
Energy test result is shown in Table 1.
Table 1:
By comparison it is evident that the electrolytic conductivity after mineral-modified significantly improves, and the drawing of polymer film
It stretches intensity, tearing strength and elongation at break all to increase substantially, not only improves the mechanical performance of polymer, and increase
The porosity of polymer film causes Li+ ion mobility to be accelerated, improves ionic conductivity.
Claims (10)
1. a kind of high pressure ternary lithium battery gel polymer electrolyte, it is characterised in that: mainly by following several raw materials preparation and
At: copolymer powder, organic solvent and inorganic additive.
2. high pressure ternary lithium battery gel polymer electrolyte according to claim 1, it is characterised in that: the copolymer
Powder is Kynoar-hexafluoropropene powder.
3. high pressure ternary lithium battery gel polymer electrolyte according to claim 1, it is characterised in that: described inorganic to add
Add agent for a combination of one or more in lithium carbonate, aluminium oxide, silica, magnesia, zinc oxide or titanium dioxide.
4. high pressure ternary lithium battery gel polymer electrolyte according to claim 3, it is characterised in that: described is inorganic
Additive is partial size < 150nm particle.
5. high pressure ternary lithium battery method for preparing gel polymer electrolyte according to claim 1, it is characterised in that:
The organic solvent is acetone, N, one of N dimethylformamide, N- methyl pyrrolidone or a variety of compositions.
6. a kind of preparation side of high pressure ternary lithium battery gel polymer electrolyte according to claim 1-5
Method, it is characterised in that: including the following steps:
1) copolymer powder of certain mass is dissolved in organic solvent, inorganic additive is then added, in 60-70 DEG C of temperature
It is uniformly mixed within lower heating stirring 8-10 hours, obtains coating liquid;
2) coating liquid is cast on the glass plate of smooth pieces, after coating liquid is struck off, is placed in 20-80 DEG C together with glass plate
It is separated after carrying out within 50-70 minutes in water, then is transferred in 25-60 DEG C of water and handles 8-12 hours, it is solidifying that lithium ion battery is obtained after drying
Xanthan polymer film;
3) lithium ion battery gel polymer film after -90 ° of vacuum drying 20-30 hours, is impregnated into 1-3 in the electrolytic solution at 80 °
Hour to get arrive required lithium ion battery gel polymer electrolyte.
7. high pressure ternary lithium battery method for preparing gel polymer electrolyte according to claim 6, it is characterised in that:
It is 0.5-5% that added inorganic additive, which accounts for the mass percent of obtained coating liquid, in the step 1).
8. high pressure ternary lithium battery method for preparing gel polymer electrolyte according to claim 6, it is characterised in that:
It is 5%-15% that added copolymer powder, which accounts for the mass percent of obtained coating liquid quality, in the step 1).
9. high pressure ternary lithium battery method for preparing gel polymer electrolyte according to claim 6, it is characterised in that:
The molar concentration of electrolyte in the step 3) is the .0mol/L of 1 .0~4.
10. high pressure ternary lithium battery method for preparing gel polymer electrolyte according to claim 9, feature exist
In: the electrolyte in the step 3) is LiClO4/EC-DMC solution, LiClO4/EC-PC solution, LiClO4/EC-DEC solution
At least one of.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103804708A (en) * | 2012-11-14 | 2014-05-21 | 海洋王照明科技股份有限公司 | Poly(vinylidene fluoride-hexafluoropropenyl) gel polymer film as well as preparation and application thereof |
CN103972584A (en) * | 2013-02-04 | 2014-08-06 | 苏州宝时得电动工具有限公司 | Electrolyte carrier membrane, electrolyte, preparation method of two and lithium ion battery |
CN108615936A (en) * | 2018-04-25 | 2018-10-02 | 成都新柯力化工科技有限公司 | A kind of nickelic ternary lithium battery gel polymer electrolyte and preparation method |
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- 2019-04-12 CN CN201910295108.0A patent/CN109950619A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103804708A (en) * | 2012-11-14 | 2014-05-21 | 海洋王照明科技股份有限公司 | Poly(vinylidene fluoride-hexafluoropropenyl) gel polymer film as well as preparation and application thereof |
CN103972584A (en) * | 2013-02-04 | 2014-08-06 | 苏州宝时得电动工具有限公司 | Electrolyte carrier membrane, electrolyte, preparation method of two and lithium ion battery |
CN108615936A (en) * | 2018-04-25 | 2018-10-02 | 成都新柯力化工科技有限公司 | A kind of nickelic ternary lithium battery gel polymer electrolyte and preparation method |
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Application publication date: 20190628 |