CN114539513B - Lithium battery solid electrolyte, preparation method thereof and lithium battery structure - Google Patents
Lithium battery solid electrolyte, preparation method thereof and lithium battery structure Download PDFInfo
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- CN114539513B CN114539513B CN202111289421.7A CN202111289421A CN114539513B CN 114539513 B CN114539513 B CN 114539513B CN 202111289421 A CN202111289421 A CN 202111289421A CN 114539513 B CN114539513 B CN 114539513B
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 86
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 84
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 229920000728 polyester Polymers 0.000 claims abstract description 93
- 239000000463 material Substances 0.000 claims abstract description 92
- 239000000178 monomer Substances 0.000 claims abstract description 55
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 53
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 51
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 51
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000006258 conductive agent Substances 0.000 claims abstract description 30
- -1 lithium ion compound Chemical class 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 239000000758 substrate Substances 0.000 claims description 25
- 239000003960 organic solvent Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- 229920001634 Copolyester Polymers 0.000 claims description 9
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 8
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 4
- 206010006580 Bundle branch block left Diseases 0.000 claims description 3
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 3
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 101150058243 Lipf gene Proteins 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 abstract description 21
- 229920001971 elastomer Polymers 0.000 abstract description 7
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- 230000000694 effects Effects 0.000 abstract description 5
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- 230000007613 environmental effect Effects 0.000 abstract description 4
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- 239000004622 biodegradable polyester Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
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- 238000006243 chemical reaction Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
- 238000007599 discharging Methods 0.000 description 4
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 3
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- 150000002500 ions Chemical class 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
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- 239000002244 precipitate Substances 0.000 description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
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- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
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- 230000036760 body temperature Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention relates to the technical field of lithium batteries, in particular to a solid electrolyte of a lithium battery, a preparation method of the solid electrolyte and a lithium battery structure. The lithium battery solid electrolyte comprises a lithium salt conductive agent and a bio-based polyester base material, wherein the lithium salt conductive agent is a lithium ion compound and is used for providing conductive lithium ions, the bio-based polyester base material is used for dispersing the lithium salt conductive agent and conducting the lithium ions, belongs to linear molecules, is an elastomer, is in an amorphous structure, has certain viscosity and plays a role in dispersing and bonding the lithium ions of the lithium salt stably, and due to the amorphous structure, the limit effect on the transmission of the conductive lithium ions in the lithium salt is small, so that the conductivity of the lithium battery is improved; the lithium battery has damage self-repairing capability, and the service life of the lithium battery structure can be well prolonged; the prepared monomer structure is obtained by preparing renewable biomass, so the biodegradable polyester film has biodegradability and good environmental protection performance.
Description
[ technical field ] A
The invention relates to the technical field of lithium batteries, in particular to a solid electrolyte of a lithium battery, a preparation method of the solid electrolyte and a lithium battery structure.
[ background ] A method for producing a semiconductor device
With the commercialization of lithium batteries, lithium batteries have been widely used in the fields of 3C, electric vehicles, and energy storage, particularly solid state lithium batteries. The solid electrolyte structure of a lithium battery, as an important component of a lithium battery, directly affects the conductivity and electrochemical window of the lithium battery. When the lithium battery is used, in the process of repeated charging and discharging, the transmission performance of the charged particles in the solid electrolyte directly influences the conductivity of the lithium battery, and the existing solid electrolyte material is usually prepared from a shaping body material which is easy to crystallize, so that the transmission performance of the conductive particles is poor.
[ summary of the invention ]
In order to solve the technical problems of poor transmission and poor conductive effect of conductive particles of a solid electrolyte in the prior art, the embodiment of the invention provides a solid electrolyte of a lithium battery, a preparation method of the solid electrolyte and a lithium battery structure.
The embodiment of the invention provides a solid electrolyte of a lithium battery, which comprises a lithium salt conductive agent and a bio-based polyester base material, wherein the lithium salt conductive agent is a lithium ion compound and is used for providing conductive lithium ions, the bio-based polyester base material is used for dispersing the lithium salt conductive agent and is used for conducting the lithium ions, and the general formula of the bio-based polyester base material at least comprises the following structure:
wherein:
Y 1 Included
at least one of;
Y 2 Included
at least one of;
Y 3 Included
at least one of;
x is an open carbon chain;
z is a bond linker or an open carbon chain;
q is an open carbon chain;
the sum of the number of the branched chains of X, Z and Q is less than or equal to 30 percent of the sum of s, p and m;
when in use
All without branched chain, Y 1 、Y 2 、Y 3 Is not totally made of
Forming;
s and p are not zero at the same time, and s and m are not zero at the same time.
Preferably, the bio-based polyester base material comprises a copolyester PBPSSI or a copolyester PLBSI.
Preferably, the mass ratio range of the bio-based polyester base material to the lithium salt conductive agent is as follows: 1:0.2-1:2.0.
Preferably, the lithium salt conductive agent includes LiTFSI, liPF 6 、LiBF 4 、LiAsF 6 、LiClO 4 3-MLBSB, LBNB, DCLBSB, LBOB, LBSB, LBPFPB, LBBPB, TFLBBB, TCLBSB, 3-FLBBB or LBBB.
In order to solve the above technical problems, the present invention also provides a method for preparing a solid electrolyte for a lithium battery, which is used for preparing the solid electrolyte for a lithium battery as described above, and comprises: preparing a bio-based polyester base material, and polymerizing a monomer a and a monomer b to obtain the bio-based polyester base material; wherein:
monomer a comprises
At least one of;
the monomer b comprises at least one of HOOC-Z-COOH, HO-Q-OH and HOOC-X-OH; x is an open-chain carbon chain; z is a bond linker or an open carbon chain; q is an open carbon chain; the sum of the branched chain quantity of the X, the Z and the Q is less than or equal to 15 percent of the sum of the molar quantity of the monomer a and the molar quantity of the monomer b; placing the bio-based polyester material in a dissolution vessel; adding an organic solvent to dissolve the bio-based polyester material to form a polyester mixed solution; adding a lithium salt conductive agent, and dissolving the lithium salt conductive agent in the polyester mixed solution to obtain a solid electrolyte solution.
Preferably, the method further comprises the following steps: providing an electrode structure as a substrate, and transferring the solid electrolyte solution onto the electrode structure to obtain a lithium battery solid electrolyte to be dried; and drying the lithium battery solid electrolyte to be dried under at least two preset temperature ranges and preset drying time corresponding to each preset temperature range to obtain the lithium battery solid electrolyte directly formed on the electrode structure.
Preferably, the solid electrolyte solution is transferred to the electrode structure in a dropping manner through a dropper to obtain the solid electrolyte of the lithium battery to be dried.
Preferably, the bio-based polyester material: organic solvent: the mass ratio range of the lithium salt conductive agent is 1:2-5:0.2-2.
Preferably, the organic solvent comprises one or more of N-methylpyrrolidone, chloroform or tetrahydrofuran.
In order to solve the technical problem, the invention further provides a lithium battery structure, which comprises a positive electrode structure, a solid electrolyte and a negative electrode structure which are sequentially stacked, wherein the solid electrolyte is the solid electrolyte of the lithium battery.
Compared with the prior art, the technical scheme provided by the embodiment of the invention has the beneficial effects that:
1. the bio-based polyester substrate material belongs to linear molecules, is an elastomer, is in an amorphous structure, has certain viscosity, and plays a role in dispersing and bonding lithium ions of lithium salt stably. Due to the amorphous structure, the lithium salt has small limit effect on the transmission of conductive lithium ions in the lithium salt, so that the conductivity of the lithium salt is improved. Moreover, because the lithium ion battery belongs to linear molecules and has a repairing characteristic, when the lithium ion battery is applied to a lithium battery structure, the lithium battery structure is heated when the transmission performance of lithium ions is reduced due to microscopic damage in the solid electrolyte in the process of repeated charging and discharging, so that the self-repairing of the damage can be realized, and the service life of the lithium battery structure can be well prolonged; meanwhile, the prepared monomer structure is prepared from renewable biomass, so the biodegradable polyester resin has biodegradability and good environmental protection performance.
2. The bio-based polyester base material has low crystallinity and high stability, can be well applied to the fields of flexible wearable equipment, automobile batteries and the like, and can achieve self-repairing by utilizing the working temperature of the bio-based polyester base material so as to prolong the service life of the batteries.
3. The bio-based polyester substrate material contains a large number of hydrogen bonds inside, and can be automatically repaired when the battery is damaged.
4. The bio-based polyester base material is a good amorphous elastomer, is beneficial to improving the volume expansion of a solid electrolyte during the transmission of lithium ions, and can also play the role of toughness in the field of flexible batteries. Moreover, polar groups on the molecular chain can form coordination and de-coordination with lithium ions, so that the migration of the lithium ions in the solid electrolyte is facilitated, and the rate capability is improved.
5. In the lithium battery structure provided by the invention, as the solid electrolyte structure is prepared by utilizing the bio-based polyester substrate material, the lithium battery structure has a higher electrochemical window which is more than 5V, higher ionic conductivity, high safety performance, lower impedance value in the transmission process of conductive lithium ions and higher activation energy.
[ description of the drawings ]
FIG. 1 is a schematic flow chart of a method for preparing a solid electrolyte for a lithium battery provided in a third embodiment of the present invention;
FIG. 2 is another schematic flow chart of a method for preparing a solid electrolyte for a lithium battery provided in a third embodiment of the present invention;
fig. 3 is a schematic cross-sectional view of a lithium battery structure provided in a fourth embodiment of the invention;
FIG. 4 is a schematic diagram of CV curve test of the lithium battery structure (lithium salt is LiTFSI) prepared by the present invention;
FIG. 5 shows the structure of lithium battery (lithium salt is LiClO) obtained by the present invention 4 ) Schematic diagram of CV curve test of (1);
FIG. 6 is a graph of the impedance test of the lithium battery structure (lithium salt is LiTFSI) prepared by the present invention;
FIG. 7 shows the structure of lithium battery (lithium salt is LiClO) obtained by the present invention 4 ) Impedance test graph of (a);
fig. 8 is a schematic view of a state where the obtained solid electrolyte solution is coated on a glass plate with a louver blade to scrape out a grid;
FIG. 9 is a schematic view showing a state after the scratch is observed to be apparently disappeared after heating the sample based on FIG. 8 at a constant temperature of 40 ℃ for 30 min;
FIG. 10 is a schematic view of a state where the obtained solid electrolyte solution is coated on a glass plate and observed under a magnifying glass;
FIG. 11 is a schematic view of a state observed under a magnifying glass after heating the obtained solid electrolyte solution coated on a glass plate for 10min under a constant temperature condition of 50 ℃;
FIG. 12 is a schematic view of a state of observation under a magnifying glass after the obtained solid electrolyte solution was coated on a glass plate and heated for 10min under a constant temperature condition of 50 ℃.
[ detailed description ] A
To make the objects, technical solutions and advantages of the embodiments of the present invention clearer and more complete, the technical solutions of the embodiments of the present invention will be described below, it is obvious that the described embodiments are a part of the embodiments of the present invention, rather than all of the embodiments, and the contents of the embodiments of the present invention can be arranged and designed in various different configurations.
Thus, the following detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
Example 1
The embodiment provides a solid electrolyte of a lithium battery, which includes a lithium salt conductive agent and a bio-based polyester base material, wherein the lithium salt conductive agent is a lithium ion compound for providing conductive lithium ions, the bio-based polyester base material is used for dispersing the lithium salt conductive agent and conducting the lithium ions, and a general formula of the bio-based polyester base material at least includes the following structure:
"the general formula of the bio-based polyester substrate material at least comprises the structure shown in the following general formula at least
The structure "shown refers to: the bio-based polyester base material comprises at least basic structural units
The basic building blocks of the biobased polyester base material may comprise only
Other basic structural units can be contained, and all the basic structural units of the bio-based polyester base material are formed in a random copolymerization mode.
That is, the connection manner between all the basic structural units of the bio-based polyester-based base material is not limited, and the actual molecular structure of the bio-based polyester-based base material may be the permutation and combination of the connection manner of the basic structural units.
The bio-based polyester-based base material provided by the embodiment belongs to linear molecules, is an elastomer, is in an amorphous structure, has certain viscosity, and plays a role in dispersing and stably bonding lithium ions of lithium salt. Due to the amorphous structure, the lithium salt has small limit effect on the transmission of conductive lithium ions in the lithium salt, so that the conductivity of the lithium salt is improved. Moreover, because the lithium ion battery belongs to linear molecules and has a repair characteristic, when the lithium ion battery is applied to a lithium battery structure, the lithium battery structure is heated when the transmission performance of lithium ions is reduced due to damage in the solid electrolyte in the process of repeated charging and discharging, and the service life of the lithium battery structure can be well prolonged.
In the structure of the bio-based polyester base material, Y 1 Included
Are all Y 1 Specific forms of presence are possible in the structure of the bio-based polyester substrate material.
Y 2 Included
Are all Y 2 Specific forms of presence are possible in the structure of the bio-based polyester substrate material.
Y 3 Included
Are all Y 3 Possible specific forms of presence in the structure of the bio-based polyester substrate material.
It is to be noted that, in the structure of the bio-based polyester base material, Y is 1 、Y 2 And Y 3 All three of the three can only have one specific existence form, and also can have a plurality of specific existence forms coexisting. Specifically, in the structure of the bio-based polyester base material, all of Y 1 May be the same, e.g. both are
Both forms of Y may also be present 1 E.g. co-existing
Of course, more forms may be present at the same time. Y is 2 And Y 3 The same is true. That is, in the structure of the bio-based polyester base material, though Y is a basic structural unit 1 、Y 2 、Y 3 Can only be one of the above-mentioned specific forms, but there are a large number of basic structural units in the biobased polyester base material, even if they belong to different basic structural units
This basic building block, but their respective Y 1 Can be different, e.g. in a basic building block
Middle Y 1 Is that
In another basic structural unit
Y 1 Is that
Y 2 And Y 3 The same is true.
In general, in the structure of the bio-based polyester base material, Y may exist in a plurality of existing forms at the same time 1 、Y 2 、Y 3 In the basic structural unit
Each of
Y of (A) is 1 Are relatively independent in terms of their selection of basic building blocks
Each of
Y of (A) is 2 Are relatively independent in terms of their selection of basic building blocks
Each of
Y of (A) is 3 The selection of the two groups of the organic acid compounds is relatively independent, and the connection combination mode of the two groups of the organic acid compounds is also random, and the combination can be carried out in a permutation combination mode.
Wherein X is an open carbon chain, Z is a linker or an open carbon chain, and Q is an open carbon chain. It is noted that "open carbon chain" as referred to herein includes open carbon chains with branching, open carbon chains without branching, and-CH 2-. For example: x may be-CH 2-or may be
-CH2-, etc., and is not limited thereto, and Z and Q are the same.
When Z is a bonded linker, Z is attached between two groups such that the two groups are connected by a chemical bond. Such as when Y 2 Is composed of
And a basic structural unit
Is composed of
In this case, Z is a bond linker.
When at least one of X, Z and Q has a branched chain, the sum of the branched chains of X, Z and Q is less than or equal to 30% of the sum of s, p and m. It is understood that the sum of the number of branches of X, Z and Q may be 15%, 10% or less of the sum of s, p and m, and the like, without being limited thereto.
By controlling the number of the branched chains, the rigidity of the bio-based polyester substrate material can be effectively controlled, and the molecules of the bio-based polyester substrate material are ensured to have enough fluidity and amorphous performance, so that the self-repairing of the damage can be smoothly realized. Preferably, the sum of the number of branches of X, Z and Q is less than or equal to 10% of the sum of s, p and m.
It should be noted that when
When none of them contains branched chain, Y 1 、Y 2 、Y 3 Is not totally composed of
And (4) forming. Designed in such a way as to utilize
The structures provide certain steric hindrance, and the self-healing material has excellent flow characteristics due to the reduction of molecular crystallization, can smoothly exert the self-healing function, and better improves the transmission performance of conductive lithium ions, thereby improving the conductivity. In addition to this, the present invention is,
the isostructures are also beneficial to reducing the self-repairing temperature of the self-repairing material, so that the scratch self-healing can be completed at lower temperature.
To further getImprove self-repairing capability and reduce self-repairing temperature, structure
The sum of the number of the three is more than or equal to 10 percent of the sum of s, p and m. It can be understood that the structure
The sum of the number of the three may be 12%, 15%, etc. or more of the sum of s, p and m, and is not limited thereto.
The self-healing temperature of the bio-based polyester base material can be adjusted to be close to the body temperature of a human body, so that when the bio-based polyester base material is applied to consumer electronics and wearable equipment, even if the battery performance of the product is reduced, a user can enable the temperature near the product to be close to 37 ℃ in the normal use process, the self-healing of the product is completed in the normal use process of the user, and the product does not need to be specially repaired. Therefore, the convenience and the practicability of the product are greatly improved, the original appearance of the product is better protected, the high attractiveness can be kept after long-time use, the maintenance cost is greatly reduced, and the good conductive performance of the product can be continuously kept
Or when the lithium battery structure with the bio-based polyester base material is applied to an electric vehicle or other large-scale electronic equipment, the heat generated by the work of the engine is transferred to the battery pack to reach the repair temperature, so that the damaged lithium battery structure is repaired.
It is to be noted that
Refers to all of these structures contained throughout the bio-based polyester substrate material to
For example, when Y 2 Is composed of
Time and Y 2 Is composed of
When the utility model is used, the water is discharged,
therein all are provided with
With this configuration, then these need to be counted. The statistics of the other two structures are the same.
Furthermore, it should be noted that s and p are not zero at the same time, and s and m are not zero at the same time.
Further, in order to make the self-repairing capability of the bio-based polyester base material more stable and more prominent, the number average molecular weight of the bio-based polyester base material is greater than or equal to 3w. It is understood that the number average molecular weight of the bio-based polyester substrate material may also be greater than or equal to 5w, 8w, 9w, 10w, etc., and is not limited thereto. Preferably, the number average molecular weight of the bio-based polyester substrate material is greater than or equal to 5w.
In some specific embodiments, the bio-based polyester base material comprises a copolyester PBPSSI or a copolyester PLBSI. The bio-based polyester (PBPSSI, PLBSI) has good adhesion and transmission performance, effectively bonds the lithium salt conductive agent to prepare the lithium ion solid electrolyte, and improves the ion transmission capability and the SEI stability. The lithium ion conductive polymer is also a good amorphous elastomer, is beneficial to improving the volume expansion of a solid electrolyte during the transmission of lithium ions, and can also play the role of toughness in the field of flexible batteries. Moreover, polar groups on the molecular chain can form coordination and de-coordination with lithium ions, so that the migration of the lithium ions in the solid electrolyte is facilitated, and the rate capability is improved.
The copolyester PBPSSI is prepared by the following monomer polymerization reaction:
butanediol, propanediol, sebacic acid, succinic acid and itaconic acid.
The copolyester PLBSI is prepared by the following monomer polymerization reaction: lactic acid, butanediol, sebacic acid and itaconic acid.
Example 2
This embodiment provides a method for preparing a bio-based polyester substrate material, including: and polymerizing the monomer a and the monomer b to obtain the bio-based polyester base material.
Wherein:
the monomer a comprises HOOC-Z-COOH,
At least one of;
the monomer b comprises at least one of HOOC-Z-COOH, HO-Q-OH and HOOC-X-OH;
x is an open carbon chain;
z is a bond linker or an open carbon chain;
q is an open carbon chain;
the sum of the branched chain quantity of the X, the Z and the Q is less than or equal to 15 percent of the sum of the molar quantity of the monomer a and the molar quantity of the monomer b.
X is an open carbon chain, Z is a linker or an open carbon chain, and Q is an open carbon chain. "open carbon chain" includes open carbon chains with branches, open carbon chains without branches, and-CH 2 -. For example: x may be-CH 2 -, may also be
-CH 2 CH 2 -and the like, and is not limited thereto, Z and Q are the same.
When Z is a bonded linker, Z is attached between two groups such that the two groups are connected by a chemical bond. For example, when the monomer b is HOOC-COOH, Z in this case is a bond linker.
The sum of the branched chain quantity of the X, the Z and the Q is controlled to be less than or equal to 15% of the sum of the molar quantity of the monomer a and the molar quantity of the monomer b, so that the molecular fluidity of the prepared bio-based polyester substrate material is ensured, the self-healing of the bio-based polyester substrate material can be smoothly realized, and the sufficient fluidity is provided for lithium ions. It is understood that the sum of the number of branches of the three of X, Z and Q may be controlled to be 10%, 5%, etc. or less of the sum of the molar amounts of the monomer a and the monomer b, and is not limited thereto. Preferably, the sum of the number of branches of the three X, Z and Q is less than or equal to 5% of the sum of the molar amounts of the monomers a and b.
In order to enable the prepared bio-based polyester base material to have better flow characteristics, further improve the transmission capability and self-healing capability of conductive lithium ions and reduce the temperature required for self-healing, the molar quantity of the monomer a is controlled to be more than or equal to 10 percent of the total molar quantity of the monomer a and the monomer b. Therefore, the prepared bio-based polyester substrate material can present better amorphous state and elastic deformation characteristic, and the transmission performance and the self-repairing capability are improved. It is to be understood that the molar amount of the monomer a may also be controlled to be greater than or equal to 20%, 30%, 40%, 50%, etc. of the total molar amount of the monomer a and the monomer b, and is not limited thereto. Preferably, the molar amount of the monomer a is controlled to be 20% or more of the total molar amount of the monomer a and the monomer b.
The bio-based polyester substrate material provided by the embodiment of the invention has biodegradability and good environmental protection performance because the prepared monomer structures are all prepared from renewable biomass.
The method comprises the following steps of polymerizing the monomer a and the monomer b:
s1: reacting the monomer a and the monomer b at the normal pressure of 60-150 ℃ for 0.5-5 h;
s2: after the step S1, reacting for 1-5 h at 140-230 ℃ under normal pressure;
s3: after the step S2, reacting for 2h-20h at the temperature of 210-270 ℃ under a reduced pressure environment (lower than normal pressure) to obtain the bio-based polyester substrate material.
In step S1, when lactic acid is present in the bio-based polyester base material, pre-polymerization of lactic acid is mainly performed, the reaction temperature may be further controlled within a range of 80 ℃ to 135 ℃, the reaction time may be further controlled within a range of 1h to 3h, and preferably, the reaction temperature is set to 130 ℃ and the reaction time is 1h to 3h.
In step S2, mainly esterification is carried out, the reaction temperature can be controlled within the range of 160-220 ℃, the reaction time can be controlled within the range of 2-3 h, and preferably, the reaction temperature is set to be 180 ℃ and the reaction time is 2-3 h.
In step S3, condensation polymerization is mainly carried out, the reaction temperature can be controlled within the range of 220-260 ℃, the reaction time can be controlled within the range of 4-10 h, and preferably, the reaction temperature is set to be 220 ℃ and the reaction time is 4-10 h.
And obtaining the bio-based polyester base material after the reaction is finished. In this case, the product may also be subjected to purification treatments, such as: and dissolving the product by using chloroform, adding cold methanol (0 ℃), precipitating the bio-based polyester base material, filtering out the precipitate, and cleaning to obtain the high-purity bio-based polyester base material. Of course, the purification method is not limited thereto.
In order to more intuitively explain the technical solution in the embodiment of the present invention, the following description is made with reference to a specific synthetic example.
[ Synthesis example 1 ]
Synthesis example 1 corresponds to the synthesis of copolyester PBPSSI.
Reacting the monomer a and the monomer b for 3 hours at 130 ℃ under normal pressure;
then reacting for 3 hours at 180 ℃ under normal pressure;
finally, reacting for 10 hours at 220 ℃ in a vacuum environment;
the reaction was dissolved in chloroform and cold methanol (0 ℃) was added and the precipitate was collected and washed clean to give a biobased polyester based base material.
Wherein the monomer a is HOOC-Z-COOH which is itaconic acid, and the monomer b is the combination of HOOC-Z-COOH and HO-Q-OH. HOOC-Z-COOH comprises sebacic acid and succinic acid, and HO-Q-OH comprises butanediol and propanediol. I.e. Z contains both- (CH) 2 ) 8 -and
two exist, and Q is-CH 2 CH 2 CH 2 CH 2 This form, the form of the presence of Z
Having a carbon-carbon double bond branch.
The mol ratio of the monomer a (the percentage of the monomer a to the total mol amount of the monomer a and the monomer b) is 20%, the mol ratio of the itaconic acid is 5%, and the mol ratio of HO-Q-OH to HOOC-Z-COOH in the monomer b is 1.1:1.
since only itaconic acid in the monomer b contains branched chains, the sum of the number of the branched chains of X, Z and Q is equal to the molar weight of the itaconic acid, and the percentage of the branched chains is 5%.
The number average molecular weight was controlled to 10w.
The preparation procedures of Synthesis examples 2 to 9 were the same as those of Synthesis example 1, but the specific synthesis parameters were different, and the synthesis parameters different from those of Synthesis example 1 in Synthesis examples 2 to 9 are shown in Table 1. The procedure was as in Synthesis example 1 except that the synthesis parameters shown in Table 1 were changed.
Table 1: synthesis parameters of Synthesis examples 2 to 9
In some specific embodiments, the ratio of the bio-based polyester base material and the lithium salt conductive agent ranges from: 1:0.2-1:2.0. Optionally, the ratio of the two may also be: 1:0.5, 1:0.8, 1:1.2, 1:1.5 or 1.1.8.
The lithium salt conductive agent comprises LiTFSI and LiPF 6 、LiBF 4 、LiAsF 6 、LiClO 4 3-MLBSB, LBNB, DCLBSB, LBOB, LBSB, LBPFPB, LBBPB, TFLBBB, TCLBSB, 3-FLBBB or LBBB.
Example 3
Referring to fig. 1, the present embodiment provides a method for preparing a solid electrolyte for a lithium battery, including the following steps:
t1, preparing a bio-based polyester base material, and polymerizing a monomer a and a monomer b to obtain the bio-based polyester base material;
t2, placing the bio-based polyester material in a dissolving container;
t3, adding an organic solvent to dissolve the bio-based polyester material to form a polyester mixed solution; and
and T4, adding a lithium salt conductive agent, and dissolving the lithium salt conductive agent in the polyester mixed solution to obtain a solid electrolyte solution.
Wherein the bio-based polyester base material in step T1 is prepared as in example 2.
In step T2, the dissolution vessel comprises a beaker, flask or other vessel.
In step T3, the organic solvent includes one or more of NMP (N-methylpyrrolidone), chloroform, tetrahydrofuran, or other organic solvents. Alternatively, the dispersion may be carried out by adding zirconium balls to a vessel using a mill or a homogenizer. Alternatively, in order to ensure sufficient dissolution, it is necessary to stir at least 4 times or more using a homogenizer.
After the bio-based polyester material is fully dissolved in the organic solvent, the lithium salt conductive agent is added. After the addition was complete, stirring was again carried out at least 4 more times.
Referring to fig. 2, the method for preparing the solid electrolyte of the lithium battery further includes the following steps:
t5, providing an electrode structure as a substrate, and transferring the solid electrolyte solution to the electrode structure to obtain a lithium battery solid electrolyte to be dried;
and T6, drying the lithium battery solid electrolyte to be dried under at least two preset temperature ranges and preset drying time corresponding to each preset temperature range to obtain the lithium battery solid electrolyte directly formed on the electrode structure.
In step T5, the electrode structure comprises a positive electrode structure, onto which the solid electrolyte solution is directly transferred to obtain a battery structure to be dried, the electrode structure directly serving as a substrate for forming the solid electrolyte. Alternatively, in some specific embodiments, the solid electrolyte solution may be transferred onto the electrode structure by using a coating process, a spraying process, or a dropping method by a dropper to obtain the lithium battery solid electrolyte to be dried.
In this example, the process transfer of dropper dropping is preferred. The thickness of the solid electrolyte structural layer is usually thinner, and the dripping amount can be well controlled by dripping through a dropper, so that the uniformity of the prepared solid electrolyte film can be well ensured, and the combination degree of the solid electrolyte film and an electrode structure is improved.
In the procedure, the operation was performed in a glove box requiring an argon atmosphere and in a vacuum drying atmosphere.
In step T6, the process needs to be performed in the glove box in step T5, and the transfer is not necessary. The two preset temperature ranges are respectively a first temperature range with a lower temperature range, a second temperature range with a sequentially increased temperature and a third temperature range.
In this embodiment, two different temperature ranges are set for drying the solid electrolyte of the lithium battery to be dried.
Wherein the first temperature range is: the drying time is 1-3 h at 25-40 ℃. Alternatively, the temperature may also be: 28 ℃, 30 ℃, 33 ℃ or 27 ℃. The drying time can also be as follows: 1.3h, 1.8h, 2.3h or 2.5h.
The second temperature range is higher than the first temperature range, and the temperature range is as follows: 55-75 ℃, and the corresponding drying time is 18-30h. Alternatively, the temperature may also be: 60 ℃, 63 ℃, 70 ℃ or 74 ℃. The drying time can also be as follows: 20h, 23h, 25h or 27h.
The bio-based polyester material: organic solvent: the range of the lithium salt conductive agent is 1:2.0-5.0:0.2-2.0. Optionally, the ratio of the three may also be: 1:3.5:0.5, 1:3.9:0.8, 1:3.8:1.2, 1:4.5:1.8.
example 4
Referring to fig. 3, the present embodiment provides a lithium battery structure 30, which includes a positive electrode structure 301, a negative electrode structure 302, and a solid electrolyte 303 disposed therebetween.
Referring to the following table and fig. 4, and the accompanying drawings, in order to illustrate the good conductivity of the lithium battery structure prepared by the present invention, several experimental groups are provided below to illustrate the specific lithium ion conductivity and electrochemical window.
The lithium battery structure prepared from the bio-based polyester material PBPSSI polyester, the organic solvent N-methylpyrrolidone and the lithium salt conductive agent LiTFSI according to the proportion can show that the scanning curve in the 0-5V interval is smooth and no electrochemical reaction peak appears under the conditions of 0-6V scanning voltage and 0.005V/s scanning speed, and the lithium battery solid electrolyte provided by the invention has good electrochemical stability. The electrochemical window reaches more than 5V, and the application requirements of the lithium ion battery can be well met.
And with further reference to figure 5, the lithium salt conductor is replaced with LiClO 4 By observing the electrochemical window test curve, the smooth scanning curve of the lithium battery in the 0-5V interval can be seen, no electrochemical reaction peak appears, and the lithium battery solid electrolyte provided by the invention has good electrochemical stability. The electrochemical window reaches more than 5V, and the application requirements of the lithium ion battery can be well met.
Referring further to fig. 6, the electrochemical impedance test is performed on the obtained lithium battery structure under the following test conditions:
frequency range: 0.01HZ-10000kHZ, excitation voltage: 10mV-50mV.
The EIS spectrum is characterized by only one oblique line, and the conductivity of the EIS spectrum is 1.88 x 10 -4 S/cm, resistance: 29.502 Ω. The conductive capability of the lithium ion solid electrolyte is high, and the impedance is low. The PBPSSI serving as a solid electrolyte material can improve the electrochemical performance and reduce the ion transmission process to a certain extentThe resistance of (1).
Further comparing FIG. 7, the lithium salt was replaced by LiClO instead of LiTFSI 4 It is obvious that the lithium ion battery comprises a semicircle and a slash, wherein an abrupt low peak appears between the semicircle and the slash, which indicates that the lithium ion battery receives larger resistance in the process of conducting lithium ions. The conductivity was 8.78 x 10 -6 S/cm, resistance: 419.35 Ω, and to some extent, it was demonstrated that the lithium salt of LiTFSI contrasts with LiClO 4 Has better electrochemical performance and reduces the resistance in the ion transfer process.
Further referring to fig. 8 and 9, in order to demonstrate that the lithium ion solid electrolyte prepared by the present invention has a good repairing performance, the solid electrolyte solution obtained in step S4 is coated on a glass plate, then a grid with a certain size is uniformly scribed by a grid knife, and after heating at a constant temperature of 40 ℃ for 30min, the scratch is observed to obviously disappear. Can well show that the material has low-temperature self-healing capability.
With further reference to fig. 10, 11 and 12, the solid electrolyte solution obtained in step S4 is coated on a glass plate, and the scratch is clearly seen to gradually disappear when observed under a magnifying glass at constant temperature of 50 ℃ every 10min, further explaining that the glass plate has better self-healing capability.
Compared with the prior art, the technical scheme provided by the embodiment of the invention has the beneficial effects that:
1. the bio-based polyester substrate material belongs to linear molecules, is an elastomer, is in an amorphous structure, has certain viscosity, and plays a role in dispersing and bonding lithium ions of lithium salt stably. Due to the amorphous structure, the lithium salt has small limit effect on the transmission of conductive lithium ions in the lithium salt, so that the conductivity of the lithium salt is improved. Moreover, because the lithium ion battery belongs to linear molecules and has a repairing characteristic, when the lithium ion battery is applied to a lithium battery structure, the lithium battery structure is heated when the transmission performance of lithium ions is reduced due to microscopic damage in the solid electrolyte in the process of repeated charging and discharging, so that the self-repairing of the damage can be realized, and the service life of the lithium battery structure can be well prolonged; meanwhile, the prepared monomer structure is obtained by preparing renewable biomass, so the biodegradable polyester film has biodegradability and good environmental protection performance.
2. The bio-based polyester base material has low crystallinity and high stability, can be well applied to the fields of flexible wearable equipment, automobile batteries and the like, and can achieve self-repairing by utilizing the working temperature of the material so as to prolong the service life of the batteries.
3. The bio-based polyester substrate material contains a large number of hydrogen bonds inside, and can be automatically repaired when the battery is damaged.
4. The bio-based polyester base material is a good amorphous elastomer, is beneficial to improving the volume expansion of a solid electrolyte during the transmission of lithium ions, and can also play the role of toughness in the field of flexible batteries. Moreover, polar groups on the molecular chain can form coordination and de-coordination with lithium ions, so that the migration of the lithium ions in the solid electrolyte is facilitated, and the rate capability is improved.
5. In the lithium battery structure provided by the invention, as the solid electrolyte structure is prepared by utilizing the bio-based polyester substrate material, the lithium battery structure has a higher electrochemical window which is more than 5V, higher ionic conductivity and high safety performance, and the impedance value and activation energy of the conductive lithium ion transmission process are lower.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A solid electrolyte for a lithium battery, comprising a lithium salt conductive agent and a bio-based polyester based base material, wherein the lithium salt conductive agent is a lithium ion compound for providing conductive lithium ions, the bio-based polyester based base material is used for dispersing the lithium salt conductive agent and for conducting the lithium ions, and the general formula of the bio-based polyester based base material at least comprises the following structure:
wherein:
Y 1 Included
at least one of; y is 2 Included
At least one of;
Y 3 Included
at least one of;
x is an open-chain carbon chain;
z is a bond linker or an open carbon chain;
q is an open carbon chain;
the sum of the branched chain quantity of X, Z and Q is less than or equal to 30 percent of the sum of s, p and m;
when in use
All without branched chain, Y 1 、Y 2 、Y 3 Is not totally made of
Forming;
s and p are not zero at the same time, and s and m are not zero at the same time.
2. The solid electrolyte for a lithium battery as claimed in claim 1, wherein the bio-based polyester base material comprises a copolyester PBPSSI or a copolyester PLBSI.
3. The solid electrolyte for a lithium battery according to claim 1, wherein the bio-based polyester base material and the lithium salt conductive agent are present in a mass ratio ranging from: 1:0.2-1:2.0.
4. The solid electrolyte for lithium battery of claim 1, wherein the lithium salt conductive agent comprises LiTFSI, liPF 6 、LiBF 4 、LiAsF 6 、LiClO 4 3-MLBSB, LBNB, DCLBSB, LBOB, LBSB, LBPFPB, LBBPB, TFLBBB, TCLBSB, 3-FLBBB or LBBB.
5. A method for preparing a solid electrolyte for a lithium battery according to any one of claims 1 to 4, comprising:
preparing a bio-based polyester base material, and polymerizing a monomer a and a monomer b to obtain the bio-based polyester base material;
wherein:
the monomer a comprises HOOC-Z-COOH,
At least one of;
the monomer b comprises at least one of HOOC-Z-COOH, HO-Q-OH and HOOC-X-OH;
x is an open carbon chain;
z is a bond linker or an open-chain carbon chain;
q is an open carbon chain;
the sum of the branched chain quantity of the X, the Z and the Q is less than or equal to 15 percent of the sum of the molar quantity of the monomer a and the molar quantity of the monomer b;
placing the bio-based polyester material in a dissolution vessel;
adding an organic solvent to dissolve the bio-based polyester material to form a polyester mixed solution;
adding a lithium salt conductive agent, and dissolving the lithium salt conductive agent in the polyester mixed solution to obtain a solid electrolyte solution.
6. The method for preparing a solid electrolyte for a lithium battery as claimed in claim 5, further comprising the steps of:
providing an electrode structure as a substrate, and transferring the solid electrolyte solution onto the electrode structure to obtain a lithium battery solid electrolyte to be dried;
and drying the lithium battery solid electrolyte to be dried under at least two preset temperature ranges and preset drying time corresponding to each preset temperature range to obtain the lithium battery solid electrolyte directly formed on the electrode structure.
7. The method for preparing a solid electrolyte for a lithium battery as claimed in claim 6, wherein the solid electrolyte solution is transferred to the electrode structure by dropping with a dropper to obtain a solid electrolyte for a lithium battery to be dried.
8. The method for preparing a solid electrolyte for a lithium battery as claimed in claim 5, wherein the bio-based polyester material: organic solvent: the mass ratio range of the lithium salt conductive agent is 1:2-5:0.2-2.
9. The method of claim 5, wherein the organic solvent comprises one or more of N-methylpyrrolidone, chloroform, and tetrahydrofuran.
10. A lithium battery structure comprising a positive electrode structure, a solid electrolyte, and a negative electrode structure, which are stacked in this order, the solid electrolyte being the lithium battery solid electrolyte according to any one of claims 1 to 4.
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| CN114539513A (en) | 2022-05-27 |
| CN114133540B (en) | 2022-10-14 |
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