CN109494411B - Low-temperature flexible polymer solid electrolyte and preparation method and application thereof - Google Patents

Low-temperature flexible polymer solid electrolyte and preparation method and application thereof Download PDF

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CN109494411B
CN109494411B CN201811283239.9A CN201811283239A CN109494411B CN 109494411 B CN109494411 B CN 109494411B CN 201811283239 A CN201811283239 A CN 201811283239A CN 109494411 B CN109494411 B CN 109494411B
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CN109494411A (en
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刘晋
林泽华
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Central South University
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
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    • H01M2300/0082—Organic polymers
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Abstract

The invention discloses a low-temperature flexible polymer solid electrolyte and a preparation method and application thereof.A low-temperature flexible polymer solid electrolyte membrane is prepared by a secondary crosslinking method, namely, a polyhydroxy organic compound and a crosslinking agent with relatively large molecular weight are subjected to primary crosslinking reaction, and then the polyhydroxy organic compound and the crosslinking agent with relatively small molecular weight are subjected to secondary crosslinking reaction, and the obtained secondary crosslinking body is compounded with alkali metal salt to obtain the low-temperature flexible polymer solid electrolyte membrane; the preparation method is simple to operate and low in cost, and the prepared electrolyte membrane has the advantages of high room temperature/low temperature ionic conductivity, good mechanical property and the like. The film is applied to all-solid-state lithium, sodium or potassium batteries, has the characteristics of high capacity, good cycle performance and the like in room temperature/low temperature environments, and develops the application field of all-solid-state batteries in low temperature environments.

Description

Low-temperature flexible polymer solid electrolyte and preparation method and application thereof
Technical Field
The invention relates to an all-solid-state battery solid electrolyte, in particular to a low-temperature flexible polymer solid electrolyte, a preparation method thereof and application thereof in an all-solid-state battery, which can obtain the all-solid-state battery electrolyte capable of normally working at the temperature below zero (-20 ℃), and belongs to the field of all-solid-state battery material preparation technology and application.
Technical Field
Since 1991, lithium ion batteries, as a novel green energy storage device, were put on the market, due to their advantages of high energy density, long service life, etc., have been widely used in the 3C field such as mobile phones and notebook computers, as well as in the field of new energy vehicles. However, the toxicity and flammability of the conventional lithium ion battery using a carbonate solution as an electrolyte become a serious safety factor hindering the application and development of the lithium ion battery, and in addition, the flowability of the liquid electrolyte also causes the lithium ion battery to need a heavy outer shell for wrapping. Therefore, light and portable lithium ion battery materials and systems with high energy density, low price and excellent safety performance have become the future development direction of the lithium ion battery industry.
The emergence of solid electrolytes meets the expectations of people for portability and safety of lithium battery materials, however, traditional inorganic solid electrolytes are very hard and brittle and are difficult to make into wearable batteries; the traditional PEO-based polymer electrolyte has the difficulty of overcoming the problem of low room-temperature conductivity and is difficult to apply to actual life. The Chinese patent (publication No. CN107069082A) uses saccharides as the material of the polymer electrolyte, reduces the preparation cost of the electrolyte, and obtains the electrolyte with good room temperature ionic conductivity, but the brittleness is obviously increased and the conductivity is reduced below room temperature (25 ℃), which is not beneficial to long-term working and use at the temperature below room temperature.
Disclosure of Invention
Aiming at the technical problems of brittleness, low conductivity and the like of the conventional solid electrolyte at low temperature, the invention aims to provide a flexible polymer solid electrolyte with high ionic conductivity and good mechanical property in a low-temperature environment below room temperature.
The second purpose of the invention is to provide a preparation method of the low-temperature flexible polymer solid electrolyte, which has the advantages of simple operation steps, low preparation cost and the like.
The third purpose of the invention is to provide the application of the low-temperature flexible polymer solid electrolyte, which is used for all-solid batteries (including lithium, sodium or potassium all-solid batteries) and can obtain the all-solid batteries which have good flexibility and can stably work in a low-temperature environment.
In order to realize the technical purpose, the invention provides a preparation method of a low-temperature flexible polymer solid electrolyte, which comprises the steps of firstly carrying out primary crosslinking reaction on a polyhydroxy organic compound and a crosslinking agent A, carrying out secondary crosslinking reaction on the obtained primary crosslinked body and a crosslinking agent B, and compounding the obtained secondary crosslinked body with an alkali metal salt to obtain the low-temperature flexible polymer solid electrolyte; wherein the ratio of the molecular weight of the crosslinking agent A to the molecular weight of the crosslinking agent B is 10 or more.
The invention utilizes two cross-linking agents with different molecular weights to cross-link polyhydroxy compounds in sequence, and utilizes the cross-linking agent with larger molecular weight to pre-cross-link, which is beneficial to cross-linking to form a stable network structure; and then, further crosslinking by using a crosslinking agent with small molecular weight, wherein the crosslinking agent is mainly used for consuming residual hydroxyl groups on polyhydroxy molecules, and a large number of experiments show that the residual hydroxyl groups are one of the main reasons for low-temperature brittleness of the organic polymer electrolyte, the low-temperature flexibility of the organic polymer electrolyte can be improved after further crosslinking, and meanwhile, hydrogen bonds can be reduced and flexible ether chains can be increased after further crosslinking, so that the activity of polymer chain segments is increased, and the ionic conductivity is improved. The invention utilizes two cross-linking agents with different molecular weights to be sequentially cross-linked with the polyhydroxy compound, can prepare the polymer flexible solid electrolyte with high low-temperature (-20 ℃) ionic conductivity and good mechanical property, and has important significance for the application of all-solid batteries in real life.
Preferably, the polyhydroxy organic compound is selected from a wide range of natural sugars, such as glucose and sucrose, or polymers composed of sugar units, such as cellulose and starch, and may be a polyol compound, such as glycerol.
In a preferred embodiment, the cross-linking agent A and the cross-linking agent B are independently selected from organic compounds containing at least one reactive functional group capable of reacting with hydroxyl, such as titanyl, borohydride, siloxyl, carboxyl, amino, epoxy, acid chloride and acid anhydride. Both the crosslinking agent A and the crosslinking agent B can be selected from crosslinking agents which are generally used in the art and comprise at least two reactive groups which can react with hydroxyl groups. However, in the present invention, the crosslinking agent A and the crosslinking agent B should satisfy the condition that the molecular weight of the crosslinking agent A is larger than that of the crosslinking agent B, otherwise it is difficult to obtain a crosslinked polymer having flexibility at low temperature. The preferred cross-linking agent A is one of 3- (2, 3-glycidoxy) propyltrimethoxysilane, borane-tetrahydrofuran, isopropyl titanate, polymethylhydrosiloxane, aniline, epoxy resin and polyacrylic acid. The preferred crosslinking agent B may be selected from the above-mentioned crosslinking agents, but it is necessary that the molecular weight of the crosslinking agent B is small relative to that of the crosslinking agent A. For example, the combination of the cross-linking agent A and the cross-linking agent B with better effect is that the cross-linking agent A is 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, and the cross-linking agent B is borane-tetrahydrofuran.
Preferably, the ratio of the amount of the polyhydroxy organic compound to the total amount of the cross-linking agent A and the cross-linking agent B is 5:1 to 1: 5. The ratio of the polyhydroxy organic compound to the cross-linking agents A and B is controlled within a proper range, thereby facilitating the dehydroxylation of the polyhydroxy compound and simultaneously forming a certain degree of network polymer.
In a more preferable embodiment, the mass ratio of the crosslinking agent A to the crosslinking agent B is 20:1 to 1: 20. The proportion of the cross-linking agent A and the cross-linking agent B is controlled in a proper range, so that the ionic conductivity can be optimized, and the polymer is prevented from being agglomerated and precipitated by the excessive small-molecule cross-linking agent.
In the preferable scheme, the temperature of the first crosslinking reaction is 25-150 ℃, and the reaction time is 4-24 h.
In the preferable scheme, the temperature of the secondary crosslinking reaction is 25-150 ℃, and the reaction time is 4-24 h.
The invention provides a preparation method of a low-temperature flexible polymer solid electrolyte, which is called a secondary crosslinking method for short. The method comprises the steps of carrying out crosslinking reaction on a polyhydroxy organic compound and a crosslinking agent which contains a functional group capable of reacting with hydroxyl and has relatively large molecular weight to obtain a primary crosslinking matrix; carrying out crosslinking reaction on the obtained primary crosslinked matrix and a crosslinking agent with relatively small molecular weight to obtain a secondary crosslinked matrix; and compounding the obtained secondary matrix and the alkali metal salt by a common method in the prior art, such as mixing in a solution form, drying and curing, so as to obtain the electrolyte with high room temperature/low temperature ionic conductivity and excellent mechanical property.
The invention takes polyhydroxy organic compound as raw material, and is easy to obtain the reticular polymer electrolyte with large molecular weight.
The salt used in the low-temperature flexible polymer solid electrolyte is common salt in an alkali metal battery. Such as lithium bistrifluoromethanesulfonimide (LiTFSI), lithium bistrifluorosulfonimide (LiFSI), lithium 4, 5-dicyano-2-trifluoromethylimidazole (LiTDI), lithium difluorophosphate (LiPF)2) Sodium trifluoromethanesulfonate (NaCF)3SO3) At least one of (1).
Preferably, the mass ratio of the secondary crosslinking matrix to the alkali metal salt is 1:5 to 10: 1. The ratio of the secondary crosslinking matrix to the alkali metal salt is controlled in a proper range, so that sufficient alkali metal ions can be ensured to play a charge transmission role, and the phenomenon that the network structure of the polymer is damaged due to excessive alkali metal salt is prevented.
In the preferable scheme, the process of compounding the secondary cross-linked body and the alkali metal salt adopts liquid phase mixing, the two are dissolved and mixed by adopting a solvent, and then drying and curing are carried out.
In the preferred scheme, the drying and curing temperature is 25-90 ℃, and the drying and curing time is 4-48 hours.
The invention also provides a low-temperature-resistant flexible solid electrolyte obtained by the preparation method.
In a preferable scheme, the low-temperature-resistant flexible solid electrolyte has flexibility in a temperature range of-40 ℃ to 120 ℃.
The invention also provides application of the low-temperature flexible polymer solid electrolyte to an all-solid-state battery.
The low-temperature flexible polymer solid electrolyte is prepared into a solid electrolyte membrane which is applied to an all-solid-state battery.
The solid electrolyte membrane prepared in the technical scheme of the invention can be assembled into various all-solid-state batteries together with a lithium ion anode, a sodium ion anode, a sulfur anode and various cathodes matched with the anode, such as a lithium cathode, a sodium cathode, a silicon cathode, a tin cathode and the like. The common property of all-solid-state batteries is low-temperature flexibility and good low-temperature conductivity.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1) the low-temperature flexible polymer solid electrolyte has good low-temperature resistance, and still maintains better flexibility and higher ionic conductivity at the low temperature below minus 20 ℃.
2) The low-temperature flexible polymer solid electrolyte is prepared from polyhydroxy organic compounds by a secondary crosslinking method, and the polymer solid electrolyte with good performance is obtained by adopting crosslinking agents with different molecular weights and a proper crosslinking sequence. Firstly, a cross-linking agent with larger molecular weight is utilized for pre-cross-linking, which is beneficial to forming a stable network structure through cross-linking; and then, further crosslinking by using a crosslinking agent with small molecular weight, wherein the crosslinking agent is mainly used for consuming residual hydroxyl groups on polyhydroxy molecules, and a large number of experiments show that the residual hydroxyl groups are one of the main reasons for low-temperature brittleness of the organic polymer electrolyte, the low-temperature flexibility of the organic polymer electrolyte can be improved after further crosslinking, and meanwhile, hydrogen bonds can be reduced and flexible ether chains can be increased after further crosslinking, so that the activity of polymer chain segments is increased, and the ionic conductivity is improved.
3) The preparation process of the low-temperature flexible polymer solid electrolyte is simple to operate, low in cost, easy to control and beneficial to large-scale production.
4) The low-temperature flexible polymer solid electrolyte has high room-temperature/low-temperature ionic conductivity and good mechanical property, and the prepared all-solid-state battery is suitable for long-term stable work in a low-temperature environment.
Drawings
FIG. 1 is a graph showing the ionic conductivity of the low-temperature flexible polymer solid electrolyte prepared in example 1 of the present invention as a function of temperature, compared with conventional PEO used commercially.
Fig. 2 shows the cycle performance of a 2025 button cell assembled by the low-temperature flexible polymer flexible solid electrolyte prepared in example 1, the lithium iron phosphate positive electrode and the lithium negative electrode at 0 ℃ and-20 ℃.
Fig. 3 is a photograph of a low-temperature flexible polymer flexible solid electrolyte membrane prepared in example 1 of the present invention.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
Example 1
Placing 1.000g of corn starch and 30.0000g of DMSO (dimethylsulfoxide) in a three-neck flask, stirring at 90 ℃ under the protection of argon until the starch is completely dissolved at the stirring speed of 500r/min, adding 1.1674g of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, and reacting at 90 ℃ for 12 hours to obtain a primary cross-linked matrix; 1.0267g of borane-tetrahydrofuran was added and reacted at 20 ℃ for 12 hours to obtain a secondary crosslinked matrix. The solution was transferred to a glove box, and 5.0000g of the synthesized product solution was added to LiTFSI and stirred for 24 hours to obtain an electrolyte solution. The electrolyte membrane obtained after drying and curing the electrolyte solution was assembled into a steel-steel button cell, the ionic conductivity was measured at 0 ℃ to 120 ℃, and compared with conventional PEO as shown in fig. 1. A button cell is assembled by taking lithium iron phosphate as a positive electrode and Li as a negative electrode, the cycling performance is tested at low temperature (0 ℃ and minus 20 ℃), the capacity exertion reaches 119.6mAh/g at 0 ℃, the capacity exertion reaches 57.4mAh/g at minus 20 ℃ is shown in figure 2, and a solid electrolyte membrane substance is shown in figure 3.
Example 2
Different ratios of cross-linking agents are used in this example. Placing 1.000g of corn starch and 30.0000g of DMSO (dimethylsulfoxide) in a three-neck flask, stirring at 90 ℃ under the protection of argon until the starch is completely dissolved at the stirring speed of 500r/min, adding 0.2917g of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, and reacting at 90 ℃ for 12 hours to obtain a primary cross-linked matrix; 4.1068g of borane-tetrahydrofuran was added and reacted at 20 ℃ for 12 hours to obtain a secondary crosslinked matrix. The solution was transferred to a glove box, and 5.0000g of the synthesized product solution was taken and added to LiTDI to stir for 24 hours to obtain an electrolyte solution. The electrolyte membrane obtained after the electrolyte solution is dried and solidified is assembled into a button cell by taking lithium iron phosphate as a positive electrode and Li as a negative electrode, the cycle performance is tested at 0 ℃, the capacity is kept at 105.4mAh/g after 10 cycles of cycle,
example 3
In this example, different cross-linking agents were used. Putting 0.5000g of glycerol into a three-neck flask, stirring for half an hour at 60 ℃ under the protection of argon at the stirring speed of 500r/min, and then adding 1.1754g of polymethylhydrosiloxane to react for 10 hours at 25 ℃ to obtain a primary crosslinking matrix; 1.2778g of aniline was added and reacted at 40 ℃ for 12 hours to obtain a secondary crosslinked matrix. The solution was transferred to a glove box, and 5.0000g of the synthesized product solution was added to LiTFSI and stirred for 24 hours to obtain an electrolyte solution. And (3) drying and curing the electrolyte solution to obtain an electrolyte membrane, assembling the electrolyte membrane into a button battery by taking sulfur as a positive electrode and Li as a negative electrode, and performing charge-discharge circulation at 0 ℃, wherein the discharge capacity of the first circle is 1083mAh/g, and the capacity after 10 circles of circulation is 770 mAh/g.
Example 4
In this example, sodium-sulfur batteries were assembled using different cross-linking agents. Placing 0.5000g of cellulose into a three-neck flask, stirring for half an hour at 90 ℃ under the protection of argon at the stirring speed of 500r/min, and then adding 1.8942g of phloroglucinol triglycidyl ether epoxy resin to react for 12 hours at 70 ℃ to obtain a primary crosslinking matrix; 2.2778g of isopropyl titanate were added and reacted at 70 ℃ for 12 hours to obtain a secondary crosslinked matrix. The solution was transferred to a glove box, and 5.0000g of the synthesized product solution was taken and added to NaCF3SO3Stirring was carried out for 24 hours to obtain an electrolyte solution. Drying and solidifying the electrolyte solution to obtain an electrolyte membrane, and filling the electrolyte membrane with sulfur as a positive electrode and Na as a negative electrodeThe material is prepared into a button cell, and the charge and discharge cycle is carried out at 0 ℃, the discharge capacity of the first circle is 785mAh/g, and the capacity after 10 cycles of the cycle is 560 mAh/g.
The following examples are comparative and are not included in the context of the present invention.
Comparative example 1
This example assumes a single cross-linking. Putting 0.5000g of glycerol into a three-neck flask, adding 0.1754g of polymethylhydrosiloxane under the protection of argon gas, and reacting at 25 ℃ for 10 hours to obtain a cross-linked matrix; the solution was transferred to a glove box, and 5.0000g of the synthesized product solution was added to 0.5743g of lithium salt and stirred for 24 hours to obtain an electrolyte solution. The electrolyte solution is heated and solidified, but the electrolyte is brittle and easy to disperse, and the film formation is difficult, so that the electrolyte can not be used as a solid electrolyte.
Comparative example 2
In this example, the crosslinking is carried out with a small-molecule crosslinking agent and then with a large-molecule crosslinking agent. Placing 0.5000g of corn starch and 30.0000g of DMSO in a three-neck flask, stirring at 90 ℃ under the protection of argon at the stirring speed of 500r/min until the starch is completely dissolved, then cooling to 20 ℃, adding 1.0267g of borane-tetrahydrofuran, and reacting at 20 ℃ for 12 hours to obtain a primary crosslinking matrix. Then heating to 90 ℃, adding 1.1674g of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, reacting for 12 hours at 90 ℃, and the matrix can generate agglomeration and precipitation during the reaction process and can not be used as electrolyte.
Comparative example 3
This example uses a conventional binder to improve electrolyte film forming properties. Putting 0.5000g of glycerol into a three-neck flask, adding 0.1754g of polymethylhydrosiloxane under the protection of argon gas, and reacting at 25 ℃ for 10 hours to obtain a cross-linked matrix; 0.1373g of PVDF was added and stirred until completely dissolved; the solution was transferred to a glove box, and 5.0000g of the synthesized product solution was added to 0.5743g of lithium salt and stirred for 24 hours to obtain an electrolyte solution. The electrolyte solution is heated and solidified to form an electrolyte membrane, and the ionic conductivity is only 1.52 multiplied by 10 when the ionic conductivity is measured at 0 DEG C-7S/cm; the button cell is assembled by taking the lithium iron phosphate as the anode and the Li as the cathode, and the charge-discharge capacity is only 9.2mAh/g at 0 ℃.

Claims (6)

1. A preparation method of a low-temperature flexible polymer solid electrolyte is characterized by comprising the following steps: carrying out primary crosslinking reaction on a polyhydroxy organic compound and a crosslinking agent A, carrying out secondary crosslinking reaction on the obtained primary crosslinked body and a crosslinking agent B, and compounding the obtained secondary crosslinked body with an alkali metal salt to obtain the compound; wherein the ratio of the molecular weight of the cross-linking agent A to the molecular weight of the cross-linking agent B is more than 10; the polyhydroxy organic compound is at least one of polyalcohol and saccharide; the cross-linking agent A and the cross-linking agent B are independently selected from organic compounds containing at least one active functional group capable of reacting with hydroxyl in titanyl, boron hydride, silicon oxygen group, carboxyl, amino, epoxy, acyl chloride and acid anhydride; the ratio of the amount of the polyhydroxy organic compound to the total amount of the cross-linking agent A and the cross-linking agent B is 5:1 to 1: 5; the ratio of the amount of the cross-linking agent A to the amount of the cross-linking agent B is 20:1 to 1: 20.
2. The method of claim 1, wherein the method comprises the steps of: the temperature of the primary crosslinking reaction is 25-150 ℃, and the reaction time is 4-24 h; the temperature of the secondary crosslinking reaction is 25-150 ℃, and the reaction time is 4-24 h.
3. The method of claim 1, wherein the method comprises the steps of: the mass ratio of the secondary cross-linked body to the alkali metal salt is 1: 5-10: 1.
4. A low temperature flexible polymer solid electrolyte characterized by: the preparation method of any one of claims 1 to 3.
5. A low temperature flexible polymer solid state electrolyte as claimed in claim 4, wherein: the low-temperature flexible solid electrolyte has flexibility and ion conductivity within the temperature range of-40 ℃ to 120 ℃.
6. Use of a low temperature flexible polymer solid electrolyte as claimed in claim 4 or 5 in an all solid state battery.
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