CN112786961A - Biomass-based gel electrolyte, lithium ion battery, preparation method and application - Google Patents
Biomass-based gel electrolyte, lithium ion battery, preparation method and application Download PDFInfo
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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
- H01M10/056—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
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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- 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
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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a biomass-based gel electrolyte, a lithium ion battery, a preparation method and application thereof. The biomass-based gel electrolyte comprises biomass, an organic solvent and a lithium salt; wherein the biomass is in cold days; the content of the biomass is 5-40%; the percentage is the mass percentage of biomass in the biomass-based gel electrolyte. The lithium ion battery prepared by the biomass-based gel electrolyte has high safety and good electrochemical performance, and the preparation methods of the biomass-based gel electrolyte and the lithium ion battery are simple and low in cost.
Description
Technical Field
The invention relates to a biomass-based gel electrolyte, a lithium ion battery, a preparation method and application thereof.
Background
Lithium ion batteries are widely used because of their excellent volumetric and mass energy densities. At present, the electrolyte of the lithium ion battery mainly comprises an organic solvent and lithium salt. However, the organic solvent in the electrolyte is easily decomposed under high voltage or overcharge conditions to generate gas, which causes problems such as swelling and deformation of the battery, and combustion and explosion. Moreover, the electrode plates of the lithium ion battery packaged by the aluminum-plastic film have differences, so that incomplete absorption of electrolyte is easily caused, a small amount of free electrolyte can be extracted in the packaging process, the sealing performance of the lithium ion battery is poor, and the product percent of pass is reduced.
In order to improve the product yield and safety of lithium ion batteries, in the prior art, a liquid electrolyte is converted into a solid electrolyte, such as a gel polymer electrolyte. The gel-state polymer electrolyte is generally formed by a polymer matrix and an organic electrolyte or lithium salt through a solution casting method, a chemical crosslinking method and other methods to form a gel polymer network system, and liquid electrolyte molecules are fixed in the gel polymer network system. Although the gel-state polymer electrolyte solves the potential safety problems of leakage, corrosion, combustion and the like of the liquid electrolyte lithium ion battery to a certain extent, the preparation method of the gel-state polymer electrolyte is complex, high in process requirement and high in cost.
Chinese patent document CN 105428085A discloses a biomass-based colloidal electrolyte, which is prepared by taking agar as a raw material, decocting the agar in deionized water to form sol, and mixing the sol with different types of electrolytes to form the colloidal electrolyte; the biomass-based colloidal electrolyte is used in a super capacitor, and has high safety and rate capability. However, the biomass-based colloidal electrolyte is only suitable for a super capacitor and cannot be applied to the field of lithium ion batteries. When the electrolyte is used for a lithium ion battery, the aqueous electrolyte can react with an electrode material of the lithium ion battery, and the intercalation and deintercalation of lithium ions in the charge and discharge process cannot be realized, so that the electrochemical performance and safety of the lithium ion battery cannot be ensured. Moreover, there is no other information in the prior art that can indicate that electrolytes for supercapacitors are equally suitable for use in lithium ion batteries.
Therefore, it is highly desirable to provide a gel-state electrolyte with higher safety and better electrochemical performance for use in lithium ion batteries.
Disclosure of Invention
The invention aims to overcome the defects of low safety or poor electrochemical performance of an electrolyte used in a lithium ion battery in the prior art, and provides a biomass-based gel electrolyte, a lithium ion battery, a preparation method and application thereof. The lithium ion battery prepared by the biomass-based gel electrolyte has high safety and good electrochemical performance, and the preparation methods of the biomass-based gel electrolyte and the lithium ion battery are simple and low in cost.
In order to achieve the purpose, the invention provides the following technical scheme:
one of the technical schemes provided by the invention is as follows: a biomass-based gel electrolyte comprising biomass, an organic solvent, and a lithium salt;
wherein the content of the biomass is 5-40%; the percentage is the mass percentage of the biomass in the biomass-based gel electrolyte;
the biomass is in cold days.
In the invention, the content of the biomass is preferably 15-35%, preferably 20-30%, and more preferably 25%; the percentage is the mass percentage of the biomass in the biomass-based gel electrolyte.
The content of the organic solvent can be 40-80%, preferably 50-70%, and more preferably 65%; the percentage is the mass percentage of the organic solvent in the biomass-based gel electrolyte.
The content of the lithium salt can be 5-30%, preferably 10-20%; the percentage is the mass percentage of the lithium salt in the biomass-based gel electrolyte.
In the present invention, the cold days are generally commercially available. According to the conventional method, the cold day can be an extract of red algae wall breaking technology in the field, and the main component is seaweed gel. Said cold weather may contain dietary fiber, calcium and iron. The cold weather can be extracted from Gracilaria, thallus Porphyrae or Gelidium amansii.
The preparation process of the cold day can be a conventional preparation process in the field. No addition of crosslinking agents or initiators is generally required.
In the present invention, the organic solvent may be one or more of a carbonate solvent, an ether solvent, and a sulfone solvent, and is preferably a carbonate solvent, or a carbonate solvent and an ether solvent.
When the organic solvent is a carbonate solvent, a mixed solvent formed by compounding two carbonate solvents is preferred. More preferably a mixed solvent formed by compounding any two solvents of ethylene carbonate, propylene carbonate and dimethyl carbonate.
When the organic solvent is a carbonate solvent and an ether solvent, a mixed solvent formed by compounding a carbonate solvent and an ether solvent is preferred. Wherein, the carbonate solvent is preferably one of ethylene carbonate, propylene carbonate and dimethyl carbonate; the ether solvent is preferably ethylene glycol dimethyl ether or ethylene glycol diethyl ether. More preferably a mixed solvent formed by compounding propylene carbonate and ethylene glycol dimethyl ether; or a mixed solvent formed by compounding dimethyl carbonate and ethylene glycol diethyl ether; or a mixed solvent formed by compounding propylene carbonate and ethylene glycol diethyl ether.
Wherein the carbonate solvent may be a cyclic carbonate solvent and/or a chain carbonate solvent.
The cyclic carbonate solvent can be one or more of ethylene carbonate, propylene carbonate and gamma-butyrolactone; preferably ethylene carbonate or propylene carbonate.
The chain carbonate solvent can be one or more of methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, methyl formate, ethyl formate, methyl acetate, ethyl acetate, n-propyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, methyl butyrate and ethyl butyrate; dimethyl carbonate is preferred.
Wherein, the ether solvent can be one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1, 3-dioxolane, 1, 3-dioxane, 1, 4-dioxane, tetrahydrofuran and 2-methyltetrahydrofuran, and preferably ethylene glycol dimethyl ether or ethylene glycol diethyl ether.
Wherein the sulfone solvent can be one or more of dimethyl sulfoxide, sulfolane and dimethyl sulfone.
Wherein, when the organic solvent is a mixed solvent formed by compounding two carbonate solvents, the mass percentage ratio of the organic solvent is preferably 1: (0.67-1.5).
When the organic solvent is a mixed solvent formed by compounding a carbonate solvent and an ether solvent, the ratio of the carbonate solvent to the ether solvent in percentage by mass is preferably 1: (0.67-1.5). For example, when the organic solvent is propylene carbonate and ethylene glycol dimethyl ether, the ratio of the propylene carbonate to the ethylene glycol dimethyl ether is 1: 1.5. when the organic solvent is dimethyl carbonate and ethylene glycol diethyl ether, the mass percentage ratio of the dimethyl carbonate to the ethylene glycol diethyl ether can be 1: 1. when the organic solvent is propylene carbonate and ethylene glycol diethyl ether, the mass percentage ratio of the dimethyl carbonate to the ethylene glycol diethyl ether can be 1: 1.
in the present invention, the lithium salt may be LiY;
wherein Y can be PF6 -、CH3SO3 -、SCN-、BF4 -、ClO4 -、NO3 -、[O3SCF2CF3]-、AsF6 -、AlCl4 -、(CF3SO2)2N-、(FSO2)2N-、CF3SO3 -、B(OC2O2)2 -、(OC2O2)F2B-、(C3F6SO2)(FSO2)N-Or [ (CF)3SO2)(n-C4F9SO2)N]-(ii) a Preferably PF6 -、ClO4 -Or (CF)3SO2)2N-。
The concentration of the lithium salt is 0.5-1.5 mol/L, and the concentration is the concentration of the lithium salt in the organic solvent and the lithium salt.
In the present invention, the biomass-based gel electrolyte preferably includes 10% LiTFSI (i.e., LiN (CF)3SO2)2) 20% of cold day and 70% of organic solvent; wherein the organic solvent is prepared from the following components in a mass ratio of 1: 1.5 propylene carbonate and ethylene glycol dimethyl ether;
alternatively, the biomass-based gel electrolyte preferably comprises 10% LiClO425% of wintertime and 65% of organic solvent; wherein the organic solvent is prepared from the following components in a mass ratio of 1: dimethyl carbonate and ethylene glycol diethyl ether of 1;
alternatively, the biomass-based gel electrolyte preferably comprises 10% LiTFSI (i.e., LiN (CF)3SO2)2) 25% of wintertime and 65% of organic solvent; wherein the organic solvent is prepared from the following components in a mass ratio of 1: 1 propylene carbonate and ethylene glycol diethyl ether;
the percentage is the mass percentage of each component in the total mass of the biomass-based gel electrolyte.
The second technical scheme provided by the invention is as follows: a preparation method of a biomass-based gel electrolyte comprises the following steps: mixing the organic solvent, the lithium salt and the biomass to obtain the biomass-based gel electrolyte.
The operation and conditions of the mixing may be conventional in the art, and generally may be uniform.
The mixing temperature is preferably 30-50 ℃.
The order of addition of the organic solvent, the lithium salt and the biomass may be an order of addition conventional in the art, for example, the lithium salt and the biomass are added to the organic solvent in sequence.
The third technical scheme provided by the invention is as follows: use of a biomass-based gel electrolyte as hereinbefore described in a lithium ion battery.
The fourth technical scheme provided by the invention is as follows: a lithium ion battery comprising a biomass-based gel electrolyte as previously described.
The lithium ion battery may be a lithium ion battery conventional in the art, such as a lithium ion battery including a separator or a lithium ion battery not including a separator.
The fifth technical scheme provided by the invention is as follows: a method of making a lithium ion battery as described above, when the lithium ion battery includes a separator, comprising the steps of:
A1. adding the biomass-based gel electrolyte into the encapsulated battery cell, and standing to obtain the lithium ion battery comprising the biomass-based gel electrolyte; the battery core is prepared by alternately stacking a positive pole piece and a negative pole piece, mutually separating the pole pieces by adopting a reticular diaphragm and prepressing the diaphragm;
A2. forming and finishing the lithium ion battery comprising the biomass-based gel electrolyte;
when the lithium ion battery does not comprise the diaphragm, the preparation method of the lithium ion battery comprises the following steps:
B1. coating the biomass-based gel electrolyte on a positive pole piece or a negative pole piece, drying to obtain an electric core, and packaging the electric core to obtain a lithium ion battery comprising the biomass-based gel electrolyte; wherein the drying temperature is 80-120 ℃;
B2. and (3) forming and finishing the lithium ion battery comprising the biomass-based gel electrolyte.
In the step a1, the biomass-based gel electrolyte is added to the encapsulated battery cell, so that the active material on the positive electrode plate and the active material on the negative electrode plate are sufficiently soaked by the biomass-based gel electrolyte, and the meshes of the mesh diaphragm are filled with the biomass-based gel electrolyte.
The material of the mesh-shaped diaphragm is preferably glass fiber, nylon or polyester silk.
In step a1, the preparation method of the positive electrode sheet may be a preparation method conventional in the art. For example, the positive electrode active material is subjected to die cutting by a wet process or a dry process to obtain the positive electrode sheet.
In step a1, the preparation method of the negative electrode plate may be a preparation method that is conventional in the art. For example, the negative electrode active material is die-cut by a wet process or a dry process to obtain a negative electrode sheet.
The temperature of the rest may be a rest temperature conventional in the art, for example 25 ℃. The standing time can be 12-48 h, such as 24 h.
In step B1, the preparation method of the positive electrode sheet may be a preparation method that is conventional in the art. For example, the positive electrode active material is processed by a wet process or a dry process to prepare a positive electrode sheet.
The preparation method of the negative pole piece can be a conventional preparation method in the field. For example, the negative electrode active material is processed by a wet process or a dry process to prepare a negative electrode sheet.
The preparation method of the battery core can be conventional in the field, for example, the battery core is prepared by drying the positive pole piece or the negative pole piece coated with the biomass-based gel electrolyte, and then performing die cutting and lamination.
In the step A1 or B1, the wet process can be that the active material, the conductive agent and the adhesive are added into the solvent, the mixture is stirred evenly to obtain slurry, the slurry is coated on the surface of the foil, the primary pole piece is obtained after drying, and the pole piece is obtained after rolling and die cutting. The dry process can be mixing the active material, the conductive agent and the adhesive powder, and preparing the pole piece after slurry drawing, coating, drying and rolling.
In step a1 or B1, the packaging can be conventional in the art, such as a hard pack or a soft pack.
When the packaging is a hard package, the packaged battery cell is preferably placed in a battery shell, and then the biomass-based gel electrolyte is injected. When the package is a flexible package, it is preferably top-sealed and then impregnated with a biomass-based gel electrolyte as previously described.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
(1) the lithium ion battery prepared by the biomass-based gel electrolyte has good electrochemical performance, for example, the lithium ion battery is subjected to charge-discharge circulation at 0.5C multiplying power, the interval of each circulation is 30 minutes, and after 10 weeks of circulation, the capacity retention rate can be more than 90%;
(2) the lithium ion battery prepared by the biomass-based gel electrolyte has high safety and no fire or explosion phenomenon;
(3) the preparation method of the biomass-based gel electrolyte is simple and low in cost.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1
Preparation of biomass-based gel electrolyte
(1) Positive electrode material
Adopting a wet process to prepare a positive active material lithium iron phosphate (LiFePO)4) Mixing the conductive carbon black and the binder PVDF, adding the mixture into a solvent N-methyl pyrrolidone (NMP), uniformly stirring, coating the mixture on an aluminum current collector, and rolling and die-cutting to obtain the positive pole piece.
(2) Negative electrode material
The preparation method comprises the steps of mixing a negative active material graphite, conductive carbon black, sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) by adopting a wet process, adding the mixture into solvent deionized water, uniformly stirring, coating the mixture on a copper current collector, and rolling and die-cutting to obtain the negative pole piece.
(3) Biomass-based gel electrolyte
At the temperature of 35 ℃, mixing a mixture of 1: 1.5, mixing the propylene carbonate and the ethylene glycol dimethyl ether, adding 10 percent of LiTFSI and 20 percent of powdery agar, and uniformly mixing to obtain the biomass-based gel electrolyte;
wherein the percentage is the mass percentage of LiTFSI or the cold day in the total mass of the biomass-based gel electrolyte;
the concentration of LiTFSI in propylene carbonate, ethylene glycol dimethyl ether and LiTFSI was 0.6 mol/L.
(II) preparation of lithium ion batteries comprising separator
Alternately stacking the positive pole piece and the negative pole piece after being mutually separated by a reticular diaphragm, prepressing to prepare a battery core, and prepackaging to obtain a prepackaged battery; wherein, the material of the reticular diaphragm is glass fiber;
and (3) injecting the biomass-based gel electrolyte prepared in the step (I) into a pre-packaged battery, standing for 24h at 25 ℃, and forming and final sealing to prepare the lithium ion battery comprising the diaphragm.
Example 2
Preparation of biomass-based gel electrolyte
(1) Positive electrode material
The positive pole piece is prepared by mixing a positive active material NCM-111 (ternary), conductive carbon black and a binder PVDF through a dry process, and carrying out slurry drawing, coating, drying and rolling.
(2) Negative electrode material
The negative electrode active material graphite, conductive carbon black, sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) are mixed by adopting a dry process, and the negative electrode plate is prepared after slurry drawing, coating, drying and rolling.
(3) Biomass-based gel electrolyte
At the temperature of 35 ℃, mixing a mixture of 1: 1 dimethyl carbonate and ethylene glycol diethyl ether were mixed, and 10% LiClO was added4And 25% of powdery cold day, and uniformly mixing to obtain the biomass-based gel electrolyte;
wherein the percentage is LiClO4Or the mass percentage of the cold day to the total mass of the biomass-based gel electrolyte;
LiClO4in dimethyl carbonate, ethylene glycol dimethyl ether and LiClO4The concentration of (B) is 1.1 mol/L.
(II) preparation of lithium ion batteries comprising separator
Alternately stacking the positive pole piece and the negative pole piece after being mutually separated by a reticular diaphragm, prepressing to prepare a battery core, and prepackaging to obtain a prepackaged battery; wherein the material of the reticular diaphragm is nylon;
and (3) injecting the biomass-based gel electrolyte prepared in the step (I) into a pre-packaged battery, standing for 24h at 25 ℃, and forming and final sealing to prepare the lithium ion battery comprising the diaphragm.
Example 3
Preparation of biomass-based gel electrolyte
(1) Positive electrode material
Adopting a wet process to prepare the anode active material LiFePO4Mixing the conductive carbon black and the binder PVDF, adding the mixture into a solvent N-methyl pyrrolidone (NMP), uniformly stirring, coating the mixture on an aluminum current collector, and rolling and die-cutting to obtain the positive pole piece.
(2) Negative electrode material
The negative electrode active material graphite, conductive carbon black, sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) are mixed by adopting a dry process, and the negative electrode plate is prepared after slurry drawing, coating, drying and rolling.
(3) Biomass-based gel electrolyte
At the temperature of 35 ℃, mixing a mixture of 1: 1, mixing propylene carbonate and ethylene glycol diethyl ether, adding 10% of LiTFSI and 25% of powdery agar, and uniformly mixing to obtain the biomass-based gel electrolyte;
wherein the percentage is the mass percentage of LiTFSI or the cold day in the total mass of the biomass-based gel electrolyte;
the concentration of LiTFSI in propylene carbonate, ethylene glycol diethyl ether and LiTFSI was 0.7 mol/L.
(II) preparation of lithium ion battery not including separator
Coating the biomass-based gel electrolyte prepared in the step (I) on a negative electrode plate, and drying at 100 ℃;
and (3) die-cutting and laminating the positive pole piece and the negative pole piece coated with the biomass-based gel electrolyte to obtain a battery cell, packaging the battery cell, and finally sealing to obtain the lithium ion battery without the diaphragm.
Comparative example 1
In comparative example 1, 2% powdered agar was added to prepare a biomass-based gel electrolyte, and the procedure was otherwise the same as in example 1.
Comparative example 2
In comparative example 2, when preparing a biomass-based gel electrolyte, 60% powdered agar was added, and the procedure was otherwise the same as in example 1.
Comparative example 3
In comparative example 3, the biomass-based gel electrolyte was coated on the negative electrode sheet and dried at 70 ℃. The rest of the procedure was the same as in example 3. However, liquid remains on the surface of the dried negative electrode plate, and the dried negative electrode plate cannot be used for preparing a lithium ion battery.
Comparative example 4
In comparative example 4, the biomass-based gel electrolyte was coated on the negative electrode sheet and dried at 150 ℃. The rest of the procedure was the same as in example 3. However, after drying, the electrolyte film on the negative electrode sheet is decomposed, and powder remains on the surface, so that the electrolyte film cannot be used for preparing a lithium ion battery.
Effects of the embodiment
(1) Open circuit voltage testing
Performing an open circuit voltage test on the lithium ion batteries prepared in the above embodiments and comparative examples, wherein the test equipment is an Autolab electrochemical workstation;
test results show that the open-circuit voltage of the lithium ion batteries prepared in the examples 1-3 and the comparative example 1 is normal. The lithium ion battery prepared in comparative example 2 had a higher open circuit voltage.
(2) Safety test
And (4) testing standard: the method in GBT 31485-;
the method specifically comprises the following steps: the lithium ion batteries prepared by the above examples and comparative examples are penetrated through by high temperature resistant steel with the diameter of 5 mm-8 mm at the speed of (25 +/-5) mm/s from the direction vertical to the battery polar plate, and the penetrating position is preferably close to the surface of the penetrated battery. The steel needle is kept in the battery for 1min and observed;
wherein the taper angle of the needle tip of the high-temperature resistant steel needle is 45-60 degrees, and the surface of the high-temperature resistant steel needle is smooth and clean and has no rust, oxidation layer or oil stain;
the observation results are: the lithium ion batteries prepared in examples 1-3 and comparative example 2 have no ignition or explosion phenomenon. The lithium ion battery prepared in comparative example 1 had a fire phenomenon and was poor in safety.
(3) Rate capability and cycle capability test
Testing equipment: lanqi BK-7632L/60;
and (4) testing standard: GBT 31484-;
performing charge and discharge cycles on the lithium ion batteries prepared in the above examples and comparative examples at a rate of 0.5C, wherein the cycle interval is 30 minutes each time, and the cycle is 10 circles; the test results show that the capacity retention rates of the lithium ion batteries prepared in the examples 1 and 2 are both greater than 93%, the capacity retention rate of the lithium ion battery prepared in the example 3 is 92%, and the capacity retention rate of the lithium ion battery prepared in the comparative example 2 is only 70%.
The lithium ion battery prepared in the embodiment is subjected to charge-discharge circulation at a rate of 1.0C, wherein the circulation interval is 30 minutes every time, and the circulation is carried out for 10 circles; the test results show that the capacity retention rates of the lithium ion batteries prepared in the embodiments 1 and 2 are both greater than 90%, and the capacity retention rate of the lithium ion battery prepared in the embodiment 3 is 88%.
It can be seen that the lithium ion battery of comparative example 1 has poor safety although the open circuit voltage is normal. The lithium ion battery in comparative example 2 has high safety, but has a high open circuit voltage, and has a capacity retention ratio of only 70% when the battery is subjected to charge and discharge cycles at a rate of 0.5C, with cycles of 10 cycles at 30-minute intervals. The lithium ion battery prepared in the embodiment has high safety and good electrochemical performance, and the preparation methods of the biomass-based gel electrolyte and the lithium ion battery in the embodiment are simple and low in cost.
Claims (10)
1. A biomass-based gel electrolyte, comprising biomass, an organic solvent, and a lithium salt;
wherein the content of the biomass is 5-40%; the percentage is the mass percentage of the biomass in the biomass-based gel electrolyte;
the biomass is in cold days.
2. The biomass-based gel electrolyte of claim 1, wherein the biomass is present in an amount of 15 to 35%, preferably 20 to 30%, more preferably 25%;
and/or the content of the organic solvent is 40-80%, preferably 50-70%, and more preferably 65%; the percentage is the mass percentage of the organic solvent in the biomass-based gel electrolyte;
and/or, the content of the lithium salt is 5-30%, preferably 10-20%; the percentage is the mass percentage of the lithium salt in the biomass-based gel electrolyte.
3. The biomass-based gel electrolyte according to claim 1 or 2, wherein the organic solvent is one or more of a carbonate solvent, an ether solvent and a sulfone solvent, preferably a carbonate solvent, or a carbonate solvent and an ether solvent;
preferably, the carbonate solvent is a cyclic carbonate solvent and/or a chain carbonate solvent;
the cyclic carbonate solvent is preferably one or more of ethylene carbonate, propylene carbonate and gamma-butyrolactone; the chain carbonate solvent is preferably one or more of methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, methyl formate, ethyl formate, methyl acetate, ethyl acetate, n-propyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, methyl butyrate and ethyl butyrate;
the ether solvent is preferably one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1, 3-dioxolane, 1, 3-dioxane, 1, 4-dioxane, tetrahydrofuran and 2-methyltetrahydrofuran;
the sulfone solvent is preferably one or more of dimethyl sulfoxide, sulfolane and dimethyl sulfone.
4. The biomass-based gel electrolyte according to claim 3, wherein when the organic solvent is a mixed solvent formed by compounding two carbonate solvents, the mass percentage ratio of the organic solvent is 1: (0.67 to 1.5);
or, when the organic solvent is a mixed solvent formed by compounding a carbonate solvent and an ether solvent, the ratio of the carbonate solvent to the ether solvent in percentage by mass is 1: (0.67-1.5).
5. The biomass-based gel electrolyte of claim 1 or 2, wherein the lithium salt is LiY;
wherein Y is PF6 -、CH3SO3 -、SCN-、BF4 -、ClO4 -、NO3 -、[O3SCF2CF3]-、AsF6 -、AlCl4 -、(CF3SO2)2N-、(FSO2)2N-、CF3SO3 -、B(OC2O2)2 -、(OC2O2)F2B-、(C3F6SO2)(FSO2)N-Or [ (CF)3SO2)(n-C4F9SO2)N]-(ii) a Preferably PF6 -、ClO4 -Or (CF)3SO2)2N-；
Preferably, the concentration of the lithium salt is 0.5-1.5 mol/L, and the concentration is the concentration of the lithium salt in the organic solvent and the lithium salt.
6. The biomass-based gel electrolyte of claim 1, wherein the biomass-based gel electrolyte comprises 10% LiN (CF)3SO2)220% of cold day and 70% of organic solvent; wherein the organic solvent is prepared from the following components in a mass ratio of 1: 1.5 propylene carbonate and ethylene glycol dimethyl ether;
alternatively, the biomass-based gel electrolyte comprises 10% LiClO425% of wintertime and 65% of organic solvent; wherein the organic solvent is prepared from the following components in a mass ratio of 1: dimethyl carbonate and ethylene glycol diethyl ether of 1;
alternatively, the biomass-based gel electrolyte comprises 10% LiN (CF)3SO2)225% of wintertime and 65% of organic solvent; wherein the organic solvent is prepared from the following components in a mass ratio of 1: 1 propylene carbonate and ethylene glycol diethyl ether;
the percentage is the mass percentage of each component in the total mass of the biomass-based gel electrolyte.
7. A method for preparing a biomass-based gel electrolyte according to any one of claims 1 to 6, comprising the steps of: mixing an organic solvent, lithium salt and biomass to obtain a biomass-based gel electrolyte;
the mixing temperature is preferably 30-50 ℃.
8. Use of a biomass-based gel electrolyte according to any one of claims 1 to 6 in a lithium ion battery.
9. A lithium ion battery comprising the biomass-based gel electrolyte of any one of claims 1 to 6;
the lithium ion battery is a lithium ion battery comprising a diaphragm or a lithium ion battery not comprising a diaphragm.
10. A method of manufacturing the lithium ion battery according to claim 9,
when the lithium ion battery comprises the diaphragm, the preparation method of the lithium ion battery comprises the following steps:
A1. adding the biomass-based gel electrolyte into the encapsulated battery cell, and standing to obtain the lithium ion battery comprising the biomass-based gel electrolyte; the battery core is prepared by alternately stacking a positive pole piece and a negative pole piece, mutually separating the pole pieces by a reticular diaphragm and prepressing the pole pieces; the material of the reticular membrane is preferably glass fiber, nylon or polyester yarn; the standing time is preferably 12-48 h, and more preferably 24 h;
A2. forming and finishing the lithium ion battery comprising the biomass-based gel electrolyte;
when the lithium ion battery does not comprise the diaphragm, the preparation method of the lithium ion battery comprises the following steps:
B1. coating the biomass-based gel electrolyte on a positive pole piece or a negative pole piece, drying to obtain an electric core, and packaging the electric core to obtain a lithium ion battery comprising the biomass-based gel electrolyte; wherein the drying temperature is 80-120 ℃;
B2. and (3) forming and finishing the lithium ion battery comprising the biomass-based gel electrolyte.
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Application publication date: 20210511 |