CN116845348A - Nanogel electrolyte of flexible three-dimensional network and preparation method and application thereof - Google Patents
Nanogel electrolyte of flexible three-dimensional network and preparation method and application thereof Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 13
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012528 membrane Substances 0.000 claims description 32
- 239000002121 nanofiber Substances 0.000 claims description 28
- 229920001577 copolymer Polymers 0.000 claims description 18
- 229920000131 polyvinylidene Polymers 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 16
- 238000009987 spinning Methods 0.000 claims description 14
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 6
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 4
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims description 2
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 claims description 2
- 239000011245 gel electrolyte Substances 0.000 abstract description 10
- 210000001787 dendrite Anatomy 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract 1
- 230000005012 migration Effects 0.000 abstract 1
- 238000007711 solidification Methods 0.000 abstract 1
- 230000008023 solidification Effects 0.000 abstract 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000012621 metal-organic framework Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000010416 ion conductor Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000005486 organic electrolyte Substances 0.000 description 3
- 239000012510 hollow fiber Substances 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 108010025899 gelatin film Proteins 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013105 nano metal-organic framework Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- 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
- H01M2300/0085—Immobilising or gelification of electrolyte
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a flexible three-dimensional network nanogel electrolyte, a preparation method and application thereof, wherein the gel electrolyte with a flexible three-dimensional network structure is prepared by adopting an electrostatic spinning one-step method, no additional sintering or cross-linking solidification is needed, the preparation method is simple, the prepared nanogel electrolyte has high energy density, high ion conductivity, low body impedance and long-time stable circulation efficiency, excellent flexibility is maintained, the technical problems of low ion migration number and low ion conductivity of the gel electrolyte are solved on the basis of widening the working voltage and the use limit temperature range of the electrolyte, the generation of dendritic lithium dendrites is effectively stopped, and the interface impedance performance is improved.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a nanogel electrolyte of a flexible three-dimensional network, and a preparation method and application thereof.
Background
The organic electrolyte of the lithium ion battery widely applied to the market at the present stage has the risks of low flash point, inflammability, easy leakage and the like, so that the lithium ion battery is usedIn the process, the lithium dendrite grows to pierce the diaphragm, and the cathode is subjected to oxidation reaction to accumulate a large amount of heat energy, so that the safety problem is caused; the traditional method has the advantages that the safety is improved by adding the flame retardant, the ionic liquid and the like into the organic electrolyte, the electrochemical performance of the battery is sacrificed, and the improvement degree of the safety of the battery is limited. Compared with organic electrolyte, the nano gel electrolyte can effectively improve the heat resistance of the electrolyte, widen the working voltage range of the battery, avoid dendrites formed by lithium ion deposition from penetrating through an SEI film, and reach the ion conductivity of 10 -3 S/m.
The patent CN202210197917.X is to dissolve nitrate in organic solvent and mix with PVP, PAN or PVA solution, prepare fiber film through high-voltage electrostatic spinning, then get the continuous fast ion conductor of structure after sintering the fiber film high-temperature hot pressing; and pouring PEO, PVA or PAN solution on the surface of the fast ion conductor, drying and soaking in the electrolyte to obtain the semi-solid fast ion conductor gel electrolyte. According to the technical scheme, the electrostatic spinning technology is adopted, so that the ion conductivity of the semi-solid electrolyte can be effectively improved, but high-temperature sintering is required, secondary pouring is performed, the preparation technology is complex, and the defects that a fibrous membrane hole channel is closed easily caused by pouring PEO, PVA or PAN solution on the surface of a fast ion conductor are overcome.
The MOF material polyvinylidene chloride-hexafluoropropylene copolymer gel electrolyte prepared by the patent CN202110268579.X takes a nano MOF material as an additive, and adopts an electrostatic spinning method to prepare a MOF material polyvinylidene chloride-hexafluoropropylene copolymer nanofiber membrane; after the MOF material polyvinylidene chloride-hexafluoropropylene copolymer nanofiber membrane is soaked in lithium-sulfur electrolyte for a period of time, the excess electrolyte is absorbed, so that the MOF material polyvinylidene chloride-hexafluoropropylene copolymer gel electrolyte is prepared, but the MOF material polyvinylidene chloride-hexafluoropropylene copolymer gel electrolyte is expensive, and the preparation process of the scheme is extremely complex and difficult to realize industrial production.
The patent CN202310436201.5 adopts an electrostatic spinning method to prepare a network gel electrolyte membrane, and the semi-interpenetrating network gel membrane is formed by sequentially carrying out anion replacement and absorbing electrolyte H; the semi-interpenetrating network gel film is formed by adsorbing negatively charged monomers by hollow porous polymer nano fibers modified by quaternary ammonium salt functional groups dispersed in water, and then carrying out polymerization reaction and crosslinking reaction on the negatively charged monomers; the hollow porous polymer nanofiber modified by quaternary ammonium salt functional groups is a hollow fiber with nano through holes on the side wall, and the nano through holes are communicated with the hollow part of the hollow fiber, but the preparation process is complicated by using technical means such as crosslinking and curing, and the flexibility of the electrolyte is sacrificed.
Disclosure of Invention
The invention aims to solve the technical problems that: provides a nanogel electrolyte of a flexible three-dimensional network, a preparation method and application thereof, and aims to solve the technical problems of low ionic conductivity and poor cycle efficiency.
In order to achieve the above purpose, the invention adopts the following technical scheme: the preparation method of the nanogel electrolyte of the flexible three-dimensional network comprises the following steps:
s1: dissolving the first and second raw materials in an organic solvent and stirring for 0.5-1h to obtain spinning solution; then preparing a nanofiber membrane by a high-voltage electrostatic spinning technology; the raw material I is polyvinylidene chloride-hexafluoropropylene copolymer, the raw material II is magnesium aluminum layered double hydroxide, zinc aluminum layered double hydroxide, nickel iron layered double hydroxide, nickel aluminum layered double hydroxide, nickel iron layered double oxide or magnesium aluminum layered double oxide, and the mass ratio of the raw material I to the raw material II is 100:0.1-1;
s2: and drying the nanofiber membrane, cooling to room temperature, and then placing the cooled nanofiber membrane into electrolyte to react for 1-2 hours to prepare the nanogel electrolyte.
Based on the technical scheme, the invention can also be improved as follows:
further, the mass percentage of the polyvinylidene chloride-hexafluoropropylene copolymer in the spinning solution is 10-20%, and the mass percentage of the raw material II in the spinning solution is 0.1-1%.
Further, the polyvinylidene chloride-hexafluoropropylene copolymer has a molecular weight of 3X 10 5 -8×10 5 。
Further, the magnesium-aluminum layered double hydroxide is MgAl-LDH-OH-, mgAl-LDH-CO 3 2- 、MgAl-LDH-NO 3 - And MgAl-LDH-ClO 4 - The organic solvent is at least one of N, N-dimethylformamide and tetrahydrofuran.
Further, the technological parameters of the spinning machine in the high-voltage electrostatic spinning technology are as follows: the room temperature condition, the humidity of 30-45%, the working voltage of 10-18kV, the plate spacing of 15cm, the spinning speed of 0.1-0.3mm/min and the receiving time of 8-10h.
Further, the nanofiber membrane has a thickness of 50-500 μm and a fiber diameter of 500-2000nm.
Further, the stirring temperature in the step S1 is 50-80 ℃ and the stirring time is 10-12h; the drying temperature in the step S2 is 60-70 ℃ and the drying time is 4-8h.
Further, the preparation method of the electrolyte in the step S2 comprises the steps of dissolving lithium hexafluorophosphate in a volume ratio of 1:1 and dimethyl carbonate to prepare an electrolyte with a concentration of 1 mol/L.
The invention also discloses a preparation method of the nanogel electrolyte with the flexible three-dimensional network.
The invention also discloses application of the nanogel electrolyte in a lithium battery.
The nano gel electrolyte prepared by the invention has high energy density, high ion conductivity, low body impedance and long-time stable circulation efficiency;
1. the nanofiber membrane has a three-dimensional porous structure, can greatly improve the porosity of the fiber membrane and the liquid absorption rate of electrolyte, and increases Li + Thereby improving the ionic conductivity of the nanogel electrolyte;
2. the introduction of layered double hydroxides reduces the crystallinity of the PVDF matrix and increases the Li donor + The proportion of transmitted domains increases Li + Is not limited, the transmission efficiency of (a);
3. the interface impedance between the nanogel electrolyte and the anode and the cathode is smaller, so that the interface stability is improved, and the cycle stability and the cycle efficiency of the lithium ion battery are further improved.
Drawings
FIG. 1 is a three-dimensional network micro-topography of the nanogel electrolyte prepared in example 1;
FIG. 2 is a DSC chart of the nanogel electrolyte prepared in example 1;
FIG. 3 is an electrochemical window diagram of the nanogel electrolyte prepared in example 1;
FIG. 4 is an electrochemical impedance spectrum of the nanogel electrolyte prepared in example 1;
FIG. 5 shows a charge-discharge cycle pattern of the nanogel electrolyte prepared in example 1;
fig. 6 is a dendrite morphology diagram of the SEI film.
Detailed Description
The principles and features of the present invention are described below with reference to the drawings, the examples are illustrated for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1:
a preparation method of a nanogel electrolyte of a flexible three-dimensional network comprises the following steps:
s1: molecular weight is 5×10 5 The mass ratio of the polyvinylidene chloride-hexafluoropropylene copolymer to the magnesium aluminum layered double hydroxide is 100:0.1 is dissolved in N, N-dimethylformamide and stirred for 12 hours at 50 ℃ to ensure that the magnesium-aluminum layered double hydroxide is fully attached in a polyvinylidene chloride-hexafluoropropylene copolymer molecular chain network; transferring the mixture into a needle tube, wherein the inner diameter of the needle tube is 0.6mm, and receiving the mixture for 8 hours at room temperature by using a high-voltage electrostatic spinning machine under the conditions of 45% of humidity, 18KV of working voltage, 15cm of plate spacing and 0.15mm/min of spinning speed to prepare a nanofiber membrane with a porous three-dimensional network, wherein the thickness of the nanofiber membrane is 50 mu m, and the fiber diameter is 500nm;
s2: lithium hexafluorophosphate was dissolved in a volume ratio of 1:1, and preparing an electrolyte with the concentration of 1mol/L in a solvent formed by mixing Ethylene Carbonate (EC) and dimethyl carbonate (DMC); drying the nanofiber membrane at 60 ℃ for 8 hours, cooling to room temperature, then placing the nanofiber membrane into electrolyte to react for 2 hours, and then wiping off redundant liquid on the surface of gel by test paper to obtain the nanogel electrolyte.
Example 2:
a preparation method of a nanogel electrolyte of a flexible three-dimensional network comprises the following steps:
s1: molecular weight is 3×10 5 The mass ratio of the polyvinylidene chloride-hexafluoropropylene copolymer to the magnesium aluminum layered double hydroxide is 100:1, dissolving in tetrahydrofuran, and stirring for 10 hours at 80 ℃ to ensure that the magnesium-aluminum layered double hydroxide is fully adhered to a polyvinylidene chloride-hexafluoropropylene copolymer molecular chain network; transferring the mixture into a needle tube, wherein the inner diameter of the needle tube is 0.7mm, and receiving the mixture for 10 hours at room temperature by using a high-voltage electrostatic spinning machine under the conditions of 30% of humidity, 10KV of working voltage, 15cm of plate spacing and 0.1mm/min of spinning speed to prepare a nanofiber membrane with a porous three-dimensional network, wherein the thickness of the nanofiber membrane is 500 mu m, and the fiber diameter is 2000nm;
s2: lithium hexafluorophosphate was dissolved in a volume ratio of 1:1, and preparing an electrolyte with the concentration of 1mol/L in a solvent formed by mixing Ethylene Carbonate (EC) and dimethyl carbonate (DMC); drying the nanofiber membrane at 70 ℃ for 4 hours, cooling to room temperature, then placing the nanofiber membrane into electrolyte to react for 1 hour, and then wiping off redundant liquid on the surface of gel by test paper to obtain the nanogel electrolyte.
Example 3:
a preparation method of a nanogel electrolyte of a flexible three-dimensional network comprises the following steps:
s1: molecular weight is 8×10 5 The mass ratio of the polyvinylidene chloride-hexafluoropropylene copolymer to the magnesium aluminum layered double hydroxide is 100:0.5 is dissolved in tetrahydrofuran and stirred for 11 hours at 60 ℃ to ensure that the magnesium-aluminum layered double hydroxide is fully adhered in a polyvinylidene chloride-hexafluoropropylene copolymer molecular chain network; then transferring into needle tube, with needle head inner diameter of 0.7mm, and receiving at room temperature with high voltage electrostatic spinning machine under conditions of humidity of 40%, working voltage of 15KV, plate spacing of 15cm and spinning speed of 0.2mm/min for 9 hr to obtain the final productObtaining a nanofiber membrane with a porous three-dimensional network, wherein the thickness of the nanofiber membrane is 100 mu m, and the fiber diameter is 1000nm;
s2: lithium hexafluorophosphate was dissolved in a volume ratio of 1:1, and preparing an electrolyte with the concentration of 1mol/L in a solvent formed by mixing Ethylene Carbonate (EC) and dimethyl carbonate (DMC); drying the nanofiber membrane at 65 ℃ for 6 hours, cooling to room temperature, then placing the nanofiber membrane into electrolyte to react for 1.5 hours, and then wiping off redundant liquid on the surface of gel by test paper to obtain the nanogel electrolyte.
Comparative example:
a preparation method of a nanogel electrolyte of a flexible three-dimensional network comprises the following steps:
s1: molecular weight is 8×10 5 Dissolving polyvinylidene chloride-hexafluoropropylene copolymer in tetrahydrofuran, stirring at 60 ℃ for 11 hours, transferring into a needle tube, wherein the inner diameter of the needle tube is 0.7mm, and receiving for 9 hours at room temperature by using a high-voltage electrostatic spinning machine under the conditions of 40% of humidity, 15KV of working voltage, 15cm of plate spacing and 0.2mm/min of spinning speed to prepare a nanofiber membrane with a porous three-dimensional network;
s2: lithium hexafluorophosphate was dissolved in a volume ratio of 1:1, and preparing an electrolyte with the concentration of 1mol/L in a solvent formed by mixing Ethylene Carbonate (EC) and dimethyl carbonate (DMC); drying the nanofiber membrane at 65 ℃ for 6 hours, cooling to room temperature, then placing the nanofiber membrane into electrolyte to react for 1.5 hours, and then wiping off redundant liquid on the surface of gel by test paper to obtain the nanogel electrolyte.
Analysis of results:
FIG. 1 is a three-dimensional network micro-morphology graph of the nanogel electrolyte prepared in example 1, from which it can be seen that the fiber diameter of the nanogel electrolyte fiber membrane is between 300 and 2000nm;
FIG. 2 is a DSC chart of the nanogel electrolyte prepared in example 1, from which it can be seen that the melting enthalpy of the nanogel electrolyte membrane is reduced to 17.706J/g and the melting temperature is increased to 143.34 ℃, which illustrates that the crystallinity of the nanogel electrolyte prepared in the invention is reduced by 50% and the heat-resistant temperature is far greater than the upper limit temperature of use of a lithium ion battery;
FIG. 3 is an electrochemical window diagram of the nanogel electrolyte prepared in example 1, from which it can be seen that the electrochemical window of the nanogel electrolyte reaches 5.3V, meets the use requirement of 3.6V of the charging voltage of the lithium ion battery, and has the potential of being suitable for a high-voltage positive electrode;
FIG. 4 is an electrochemical impedance spectrum of the nanogel electrolyte prepared in example 1, from which it can be seen that the nanogel electrolyte has a bulk impedance of 2.5. Omega. And an ionic conductivity of 2X 10 -3 S/cm；
FIG. 5 is a charge-discharge cycle chart of the nanogel electrolyte prepared in example 1, from which it can be seen that the nanogel electrolyte has a discharge capacity of 128mAh/g and a charge-discharge efficiency of 97.8% when cycled 100 times at 0.5C;
FIG. 6 is a nano-gel electrolyte assembled LiFePO prepared in example 1 4 The morphology of the lithium metal negative electrode after 100 cycles of the battery is shown, and dendrites are spherical.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (10)
1. The preparation method of the nanogel electrolyte of the flexible three-dimensional network is characterized by comprising the following steps of:
s1: dissolving the first and second raw materials in an organic solvent and stirring for 0.5-1h to obtain spinning solution; then preparing a nanofiber membrane by a high-voltage electrostatic spinning technology; the raw material I is polyvinylidene chloride-hexafluoropropylene copolymer, the raw material II is magnesium aluminum layered double hydroxide, zinc aluminum layered double hydroxide, nickel iron layered double hydroxide, nickel aluminum layered double hydroxide, nickel iron layered double oxide or magnesium aluminum layered double oxide, and the mass ratio of the raw material I to the raw material II is 100:0.1-1;
s2: and drying the nanofiber membrane, cooling to room temperature, and then placing the nanofiber membrane into electrolyte to react for 1-2h to prepare the nanogel electrolyte.
2. The method for preparing the nanogel electrolyte of the flexible three-dimensional network according to claim 1, wherein the method comprises the following steps of: the mass percentage of the polyvinylidene chloride-hexafluoropropylene copolymer in the spinning solution is 10-20%, and the mass percentage of the raw material II in the spinning solution is 0.1-1%.
3. The method for preparing the nanogel electrolyte of the flexible three-dimensional network according to claim 1, wherein the method comprises the following steps of: the molecular weight of the polyvinylidene chloride-hexafluoropropylene copolymer is 3 multiplied by 10 5 -8×10 5 。
4. The method for preparing the nanogel electrolyte of the flexible three-dimensional network according to claim 1, wherein the method comprises the following steps of: the magnesium-aluminum layered double hydroxide is MgAl-LDH-OH - 、MgAl-LDH-CO 3 2- 、MgAl-LDH-NO 3 - And MgAl-LDH-ClO 4 - The organic solvent is at least one of N, N-dimethylformamide and tetrahydrofuran.
5. The method for preparing the nanogel electrolyte of the flexible three-dimensional network according to claim 1, wherein the method comprises the following steps of: the technological parameters of the spinning machine in the high-voltage electrostatic spinning technology are as follows: the room temperature condition, the humidity of 30-45%, the working voltage of 10-18kV, the plate spacing of 15cm, the spinning speed of 0.1-0.3mm/min and the receiving time of 8-10h.
6. The method for preparing the nanogel electrolyte of the flexible three-dimensional network according to claim 1, wherein the method comprises the following steps of: the thickness of the nanofiber membrane is 50-500 mu m, and the fiber diameter is 500-2000nm.
7. The method for preparing the nanogel electrolyte of the flexible three-dimensional network according to claim 1, wherein the method comprises the following steps of: the stirring temperature in the step S1 is 50-80 ℃, and the stirring time is 10-12h; the drying temperature in the step S2 is 60-70 ℃ and the drying time is 4-8h.
8. The method for preparing the nanogel electrolyte of the flexible three-dimensional network according to claim 1, wherein the method comprises the following steps of: the preparation method of the electrolyte in the step S2 comprises the steps of dissolving lithium hexafluorophosphate in a volume ratio of 1:1 and dimethyl carbonate to prepare an electrolyte with a concentration of 1 mol/L.
9. The nanogel electrolyte prepared by the method for preparing a nanogel electrolyte of a flexible three-dimensional network according to any one of claims 1 to 8.
10. Use of the nanogel electrolyte of claim 9 in a lithium battery.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117276683A (en) * | 2023-11-22 | 2023-12-22 | 吉林嘉能钠电科技有限责任公司 | Quasi-solid polymer fiber electrolyte and preparation method and application thereof |
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2023
- 2023-07-14 CN CN202310869550.6A patent/CN116845348A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117276683A (en) * | 2023-11-22 | 2023-12-22 | 吉林嘉能钠电科技有限责任公司 | Quasi-solid polymer fiber electrolyte and preparation method and application thereof |
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