CN109585910B - Solid composite electrolyte and preparation method and application of electrolyte membrane thereof - Google Patents

Solid composite electrolyte and preparation method and application of electrolyte membrane thereof Download PDF

Info

Publication number
CN109585910B
CN109585910B CN201811346058.6A CN201811346058A CN109585910B CN 109585910 B CN109585910 B CN 109585910B CN 201811346058 A CN201811346058 A CN 201811346058A CN 109585910 B CN109585910 B CN 109585910B
Authority
CN
China
Prior art keywords
attapulgite
lithium
polyurethane
solid composite
graphene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811346058.6A
Other languages
Chinese (zh)
Other versions
CN109585910A (en
Inventor
魏茂彬
李淑梅
曹健
张勇
徐婷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jilin Normal University
Original Assignee
Jilin Normal University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jilin Normal University filed Critical Jilin Normal University
Priority to CN201811346058.6A priority Critical patent/CN109585910B/en
Publication of CN109585910A publication Critical patent/CN109585910A/en
Application granted granted Critical
Publication of CN109585910B publication Critical patent/CN109585910B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0094—Composites in the form of layered products, e.g. coatings
    • 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
    • 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
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention provides a solid composite electrolyte membrane, a preparation method and application thereof, wherein the solid composite electrolyte membrane comprises the following raw materials in percentage by weight: 85-95% of waterborne polyurethane, 1-10% of lithium salt and 1-5% of amino graphene-coated attapulgite. The preparation method of the electrolyte membrane comprises the following steps: mixing and stirring water-based polyurethane and amino graphene-coated attapulgite to obtain a polyurethane composite, adding lithium salt into the polyurethane composite to obtain a lithium-doped polyurethane composite emulsion, and drying to form a film, thus obtaining the solid composite electrolyte film. The solid composite electrolyte membrane disclosed by the invention adopts the water-based polyurethane and the amino graphene coated attapulgite as the material framework of the solid composite electrolyte, so that the electrolyte is endowed with high ionic conductivity within a larger temperature range and also has good mechanical properties.

Description

Solid composite electrolyte and preparation method and application of electrolyte membrane thereof
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a solid composite electrolyte membrane and a preparation method and application of the solid composite electrolyte membrane.
Background
The lithium ion battery has the advantages of high energy density, long service life, no memory effect and the like, and is widely applied to electronic equipment such as mobile phones, computers, digital cameras, unmanned aerial vehicles, robots, sports bracelets and the like. In addition, the lithium ion battery is also used as a main energy storage device in the field of new energy automobiles to obtain better application. However, the current lithium ion battery is mainly prepared from a liquid organic electrolyte, so that potential safety hazards of easy volatilization, easy combustion, easy leakage, easy explosion and the like exist, and the development of the lithium ion battery is restricted. In order to solve the safety problem of the lithium ion battery, people adopt solid polymer electrolyte to prepare the all-solid-state lithium ion battery, so that the safety problem caused by liquid electrolyte is avoided.
Solid electrolytes for lithium ion batteries have been developed for approximately 20 years and are classified into two types, one being an organic polymer electrolyte and the other being a non-organic electrolyte. The non-organic electrolyte has the characteristic of high conductivity, but the synthesis difficulty is high, the processing is complex, the cost is too high, and the foreign related structures are researched a lot, such as Japanese Toyota, University of Tokyo, Oak Ridge National Laboratory under the department of energy of America, and the representative patent US8557445B 2. Organic polymer electrolytes are inexpensive and relatively easy to process, but almost all polymer solid electrolytes are based on polyethylene oxide (PEO). Since polyethylene oxide (PEO) can complex with salts, ions are moved by the movement of molecular chains, thereby conducting electricity. However, any solid electrolyte that is conductive through polyethylene oxide (PEO) requires heating to at least 50 degrees celsius in order to have sufficient conductivity to allow the battery to function properly. Many research institutes and companies have therefore turned their research direction to gel-type electrolytes or to make high-temperature batteries. The gel type electrolyte has high conductivity, but lacks mechanical strength, is approximately liquid, and is complicated to process.
Chinese patent publication No. CN103208651A discloses a siloxane-based solid electrolyte, its preparation and application, the components of the electrolyte comprise, by mass: 30-70% of lithium-conducting siloxane polymer, 25-40% of adhesive and 5-30% of lithium salt. The preparation method disclosed by the method comprises the following steps: dissolving a binder, a lithium salt and a siloxane polymer by an organic solvent to form a liquid substance; then coating the substrate by using a coating method; vacuum drying, forming film on the substrate, and peeling off the substrate. However, the electrolyte conduction principle disclosed in CN103208651A is that PEO ethylene oxide is substantially complexed with anions in lithium salt to form a soft mixture. The lithium ion conduction is realized by the movement of molecular chains in an amorphous state. The disadvantages are that: (1) at low temperatures, the performance of lithium ion conduction will drop dramatically, causing the battery to no longer operate; (2) the main chain of the lithium-conducting siloxane polymer is Si-O phase, and the branched chain is ethylene oxide- [ CH ] substantially2-CH2-O]n-. It is known from the published literature that lithium-conducting siloxane polymers are actually relatively low in molecular weight, less than 10000 in molecular weight, need to be produced using coating methods, and have the weakness of being not rigid.
Chinese patent publication No. CN1251347C discloses the invention patents of the us lithium energy technology company: a solid polymer electrolyte is provided which is improved in a polymer-lithium salt system to further improve ionic conductivity by adding an inorganic ion conductor (vulcanized glass powder). Since the ionic glass as a whole has high conductivity but is difficult to process, it is prepared as a powder, and by combining with a polymer-lithium salt system, simpler processing and higher conductivity are achieved, essentially achieving a compromise conductivity by adding a higher conductivity material and a lower conductivity material. The second group of polymers providing mechanical strength is smaller in mass proportion due to the higher mass proportion of the vulcanized glass powder, and therefore the mechanical properties thereof are not high; in the embodiment of the technical scheme, the micromolecule polymer and the salt solution are added into the powder for solidification, and the solid formed by the micromolecule polymer has poor mechanical property. In addition, the cost of the ion glass is high, which leads to high processing cost.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a solid composite electrolyte and a preparation method and application of an electrolyte membrane thereof, wherein the solid composite electrolyte adopts water-based polyurethane and amino graphene coated attapulgite as a material framework of the solid composite electrolyte, not only is the electrolyte endowed with high ionic conductivity in a larger temperature range, but also has good mechanical properties.
The invention provides a solid composite electrolyte, which comprises the following raw materials in percentage by weight: 85-95% of waterborne polyurethane, 1-10% of lithium salt and 1-5% of amino graphene-coated attapulgite.
Preferably, the amino graphene-coated attapulgite is obtained by mixing an amino graphene solution with purified attapulgite and then drying the mixture. Preferably, amino graphene is ultrasonically dispersed in deionized water to obtain an amino graphene solution with the concentration of 0.1-0.5 wt%, the amino graphene solution is dropwise added into purified attapulgite, the volume-to-weight ratio of the graphene solution to the attapulgite is (1-6) mL:10g, and then the mixture is dried at 75-100 ℃ to obtain the amino graphene coated attapulgite.
Preferably, the amino graphene is aminated modified graphene with amino groups on the surface. Preferably, the amino graphene is prepared by reacting oxygen with a compound of formula (I)Dissolving graphene into NMP, adding ethylenediamine, wherein the weight ratio of ethylenediamine to graphene oxide is 1:8-15, stirring and reacting at 70-90 ℃ for 3-5h, and adding a reducing agent NaBH4Reducing agent NaBH4And graphene oxide in a weight ratio of 1-2:1, stirring and reacting for 3-5h at 90-100 ℃, filtering, and washing to obtain the amino graphene.
Preferably, the method of purifying attapulgite comprises: adding water into attapulgite powder to prepare an ore pulp solution, adding sodium hexametaphosphate and sodium hydroxide, ultrasonically stirring, centrifugally separating, immersing in a sulfuric acid solution, filtering, and calcining to obtain the purified attapulgite. Preferably, the method of purifying attapulgite comprises: grinding attapulgite into powder, adding water to prepare an ore pulp solution with the concentration of 20-30 wt%, adding 1.2-1.8 wt% of sodium hexametaphosphate and 0.5-1 wt% of sodium hydroxide based on the attapulgite, ultrasonically stirring for 0.5-1h at the temperature of 30-50 ℃, immersing the attapulgite in a 4-7mol/L sulfuric acid solution according to the solid-liquid weight ratio of 1:1-3 at the temperature of 100-110 ℃ after centrifugal separation for 0.1-0.5h, performing suction filtration, drying, and calcining for 1-2h at the temperature of 300-400 ℃ to obtain the purified attapulgite.
Preferably, the synthetic raw materials of the waterborne polyurethane comprise, by weight: 35-65 parts of aliphatic polycarbonate dihydric alcohol, 18-40 parts of diisocyanate, 2-8 parts of hydrophilic chain extender, 1-5 parts of triethylamine, 0.01-0.1 part of catalyst and 250 parts of water 150-; preferably, the aliphatic polycarbonate diol is one or more of poly (1, 4-butylene carbonate) diol, poly (1, 5-pentanediol carbonate) diol, poly (1, 6-hexanediol carbonate) diol, or poly (1, 10-decanediol carbonate) diol; the diisocyanate is one or more of isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, 4 '-diphenylmethane diisocyanate or 4,4' -dicyclohexylmethane diisocyanate; the hydrophilic chain extender is dimethylolpropionic acid or dimethylolbutyric acid; the catalyst is one or more of stannous octoate, di-n-butyltin dilaurate, organic zinc or organic bismuth. Preferably, the aliphatic polycarbonate diol can be prepared by a method described in patent publication CN 102120818A.
Preferably, the method for synthesizing the aqueous polyurethane comprises: carrying out prepolymerization reaction on aliphatic polycarbonate diol and diisocyanate, adding a hydrophilic chain extender, an organic solvent and a catalyst for continuous reaction, cooling, adding triethylamine for neutralization reaction, adding water, stirring at a high speed, and removing the organic solvent to obtain the waterborne polyurethane; preferably, the diisocyanate and the aliphatic polycarbonate diol are subjected to a prepolymerization reaction at an NCO/OH ratio of 1.5 to 2.0. Preferably, the method for synthesizing the aqueous polyurethane comprises: reacting aliphatic polycarbonate diol and diisocyanate at 70-90 ℃ for 3-5h, adding a hydrophilic chain extender, NMP and a catalyst, continuing to react at 70-90 ℃ for 2-3h, cooling to 30-40 ℃, adding triethylamine for neutralization reaction, adding water, stirring at a high speed of 3000-5000r/min, and removing NMP to obtain the waterborne polyurethane.
Preferably, the lithium salt is one or more of lithium perchlorate, lithium bistrifluoromethylsulfonyl imide, lithium bifluorosulfonimide, lithium hexafluorophosphate, lithium dioxalate borate or lithium tetrafluoroborate.
The invention also provides a method for preparing the electrolyte membrane by using the solid composite electrolyte, which comprises the following steps: mixing and stirring water-based polyurethane and amino graphene-coated attapulgite to obtain a polyurethane composite, adding lithium salt into the polyurethane composite to obtain a lithium-doped polyurethane composite emulsion, and drying to form a film, thus obtaining the solid composite electrolyte film.
Preferably, the drying film forming process comprises: drying at 60-100 deg.C for 20-30h under vacuum condition.
The invention further provides an application of the solid composite electrolyte membrane prepared by the method in a lithium battery.
Compared with the prior art, the invention has the following advantages:
(1) in the solid composite electrolyte provided by the invention, the aqueous polyurethane is used as a solid electrolyte material, so that the use of solvents is reduced in the operation process, the pollution to the environment is less, and the problems of environmental protection and flammability are solved;
(2) the solid composite electrolyte provided by the invention comprises the attapulgite coated with the amino graphene, and the attapulgite and the graphene are compounded, so that the specific surface area and the porosity of the attapulgite are increased, various atoms and molecules can be adsorbed and desorbed, an ideal environment is provided for ion conduction, and the solid composite electrolyte containing the substance achieves ideal ion conductivity. The aqueous polyurethane is a copolymer with multiple blocks, has excellent comprehensive performance, and due to the difference of polarity, the soft segment and the soft segment of the aqueous polyurethane tend to form phases respectively, and the polycarbonate is selected as the soft segment, so that the ionic conductivity is ensured, and meanwhile, the electrolyte has good mechanical performance.
(2) In the solid composite electrolyte provided by the invention, in order to effectively compound the aqueous polyurethane and the attapulgite coated with the amino graphene, NCO-terminated aqueous polyurethane is obtained by controlling the reaction process of the aqueous polyurethane, and can react with the amino graphene coated on the surface of the attapulgite, so that the aqueous polyurethane and the attapulgite are effectively compounded, and the solid electrolyte membrane obtained by compounding the aqueous polyurethane and the polyurethane fully combines the excellent physicochemical properties of the attapulgite coated with the amino graphene and the aqueous polyurethane, so that the polymer solid electrolyte prepared from the aqueous polyurethane has the advantages of high mechanical strength and high conductivity.
Detailed Description
Example 1
A solid composite electrolyte comprising, in weight percent: 85% of waterborne polyurethane, 10% of lithium perchlorate and 5% of amino graphene coated attapulgite. The preparation of the solid composite electrolyte into an electrolyte membrane comprises the following steps: mixing and stirring the water-containing polyurethane and the attapulgite coated with the amino graphene according to the weight percentage to obtain a polyurethane composite, adding lithium perchlorate into the polyurethane composite to obtain a lithium-doped polyurethane composite emulsion, and drying at 60 ℃ for 30 hours under a vacuum condition to obtain the solid composite electrolyte membrane.
The waterborne polyurethane is synthesized by the following method: reacting 35 parts of poly (1, 4-butanediol carbonate) diol and 40 parts of isophorone diisocyanate at 70 ℃ for 5 hours according to parts by weight, then adding 2 parts of dimethylolpropionic acid, NMP and 0.1 part of stannous octoate, continuing to react at 70 ℃ for 3 hours, cooling to 30 ℃, then adding 5 parts of triethylamine for neutralization reaction, then adding 150 parts of water, stirring at a high speed of 3000r/min, and removing NMP to obtain the waterborne polyurethane;
the attapulgite coated with the amino graphene is obtained by mixing an amino graphene solution with purified attapulgite and then drying the mixture, specifically, dissolving graphene oxide in NMP, adding ethylenediamine, wherein the weight ratio of the ethylenediamine to the graphene oxide is 1:8, stirring the mixture at 90 ℃ for reaction for 3 hours, and adding a reducing agent NaBH4Reducing agent NaBH4Stirring and reacting the graphene oxide and the graphene oxide at a weight ratio of 2:1 at 90 ℃ for 5 hours, filtering and washing to obtain amino graphene; grinding attapulgite into powder, adding water to prepare an ore pulp solution with the concentration of 20 wt%, adding 1.8 wt% of sodium hexametaphosphate and 0.5 wt% of sodium hydroxide based on the attapulgite, ultrasonically stirring for 0.5h at 50 ℃, performing centrifugal separation, immersing the attapulgite into a sulfuric acid solution with the concentration of 7mol/L according to the solid-liquid weight ratio of 1:1 at 110 ℃ for 0.1h, performing suction filtration, drying, and calcining for 1h at 400 ℃ to obtain purified attapulgite; ultrasonically dispersing amino graphene in deionized water to obtain 0.5 wt% amino graphene solution, dropwise adding the amino graphene solution into purified attapulgite, wherein the volume-to-weight ratio of the graphene solution to the attapulgite is 1mL:10g, and drying at 100 ℃ to obtain the amino graphene coated attapulgite.
Example 2
A solid composite electrolyte comprising, in weight percent: 95% of waterborne polyurethane, 1% of lithium bis (trifluoromethyl sulfonyl imide) and 4% of amino graphene coated attapulgite. The preparation of the solid composite electrolyte into an electrolyte membrane comprises the following steps: mixing and stirring the water-containing polyurethane and the attapulgite coated with the amino graphene according to the weight percentage to obtain a polyurethane composite, adding lithium salt into the polyurethane composite to obtain a lithium-doped polyurethane composite emulsion, and drying at 100 ℃ for 20 hours under a vacuum condition to obtain the solid composite electrolyte membrane.
The waterborne polyurethane is synthesized by the following method: reacting 65 parts by weight of poly (1, 5-pentanediol carbonate) diol and 40 parts by weight of hexamethylene diisocyanate at 90 ℃ for 3 hours, adding 8 parts by weight of dimethylolbutyric acid, NMP and 0.01 part by weight of di-n-butyltin dilaurate, continuing to react at 90 ℃ for 2 hours, cooling to 40 ℃, adding 1 part by weight of triethylamine for neutralization reaction, adding 250 parts by weight of water, stirring at a high speed at the speed of 5000r/min, and removing NMP to obtain the waterborne polyurethane;
the attapulgite coated with the amino graphene is obtained by mixing an amino graphene solution with purified attapulgite and then drying the mixture, specifically, dissolving graphene oxide in NMP, adding ethylenediamine, wherein the weight ratio of the ethylenediamine to the graphene oxide is 1:15, stirring the mixture at 70 ℃ for reaction for 5 hours, and adding a reducing agent NaBH4Reducing agent NaBH4The weight ratio of the graphene oxide to the graphene oxide is 1:1, stirring and reacting for 3 hours at 100 ℃, filtering and washing to obtain amino graphene; grinding attapulgite into powder, adding water to prepare a 30 wt% ore pulp solution, adding 1.2 wt% sodium hexametaphosphate and 1 wt% sodium hydroxide based on the attapulgite, ultrasonically stirring for 1h at 30 ℃, performing centrifugal separation, immersing the attapulgite into a 4mol/L sulfuric acid solution at 100 ℃ according to a solid-liquid weight ratio of 1:3 for 0.5h, performing suction filtration, drying, and calcining for 2h at 300 ℃ to obtain purified attapulgite; ultrasonically dispersing amino graphene in deionized water to obtain an amino graphene solution with the concentration of 0.1 wt%, dropwise adding the amino graphene solution into purified attapulgite, wherein the volume-to-weight ratio of the graphene solution to the attapulgite is 6 mL:10g, and drying at 75 ℃ to obtain the amino graphene coated attapulgite.
Example 3
A solid composite electrolyte comprising, in weight percent: 90% of waterborne polyurethane, 8% of lithium bis (fluorosulfonyl) imide and 2% of amino graphene-coated attapulgite. The preparation of the solid composite electrolyte into an electrolyte membrane comprises the following steps: mixing and stirring the water-containing polyurethane and the attapulgite coated with the amino graphene according to the weight percentage to obtain a polyurethane composite, adding lithium bis (fluorosulfonyl) imide into the polyurethane composite to obtain a lithium-doped polyurethane composite emulsion, and drying at 80 ℃ for 25 hours under a vacuum condition to obtain the solid composite electrolyte membrane.
The waterborne polyurethane is synthesized by the following method: reacting 50 parts of poly (1, 6-hexanediol carbonate) glycol and 30 parts of toluene diisocyanate at 80 ℃ for 4 hours according to the parts by weight, then adding 5 parts of dimethylolpropionic acid, NMP and 0.05 part of organic zinc, continuing to react at 80 ℃ for 2.5 hours, cooling to 35 ℃, then adding 3 parts of triethylamine for neutralization reaction, then adding 200 parts of water, stirring at a high speed of 4000r/min, and removing NMP to obtain the waterborne polyurethane;
the attapulgite coated with the amino graphene is obtained by mixing an amino graphene solution with purified attapulgite and then drying the mixture, specifically, dissolving graphene oxide in NMP, adding ethylenediamine, wherein the weight ratio of the ethylenediamine to the graphene oxide is 1:10, stirring the mixture at 80 ℃ for reaction for 4 hours, and adding a reducing agent NaBH4Reducing agent NaBH4The weight ratio of the graphene oxide to the graphene oxide is 1.5:1, stirring and reacting for 4 hours at 95 ℃, filtering and washing to obtain amino graphene; grinding attapulgite into powder, adding water to prepare an ore pulp solution with the concentration of 25 wt%, adding 1.5 wt% of sodium hexametaphosphate and 0.7 wt% of sodium hydroxide based on the attapulgite, ultrasonically stirring for 0.8h at 40 ℃, performing centrifugal separation, immersing the attapulgite into a sulfuric acid solution with the concentration of 5mol/L according to the solid-liquid weight ratio of 1:2 at 105 ℃ for 0.3h, performing suction filtration, drying, and calcining for 1.5h at 350 ℃ to obtain purified attapulgite; ultrasonically dispersing amino graphene in deionized water to obtain an amino graphene solution with the concentration of 0.2 wt%, dropwise adding the amino graphene solution into purified attapulgite, wherein the volume-to-weight ratio of the graphene solution to the attapulgite is 3mL:10g, and drying at 90 ℃ to obtain the amino graphene coated attapulgite.
Example 4
A solid composite electrolyte comprising, in weight percent: 87% of waterborne polyurethane, 9% of lithium hexafluorophosphate and 4% of amino graphene coated attapulgite. The preparation of the solid composite electrolyte into an electrolyte membrane comprises the following steps: mixing and stirring the water-containing polyurethane and the attapulgite coated with the amino graphene according to the weight percentage to obtain a polyurethane composite, adding lithium hexafluorophosphate into the polyurethane composite to obtain a lithium-doped polyurethane composite emulsion, and drying at 90 ℃ for 28 hours under a vacuum condition to obtain the solid composite electrolyte membrane.
The waterborne polyurethane is synthesized by the following method: reacting 35 parts by weight of poly (1, 10-decanediol carbonate) glycol and 18 parts by weight of 4,4' -diphenylmethane diisocyanate at 90 ℃ for 4 hours, adding 4 parts by weight of dimethylolbutyric acid, NMP and 0.06 part by weight of organic zinc, continuing to react at 75 ℃ for 2.5 hours, cooling to 40 ℃, adding 4 parts by weight of triethylamine for neutralization reaction, adding 180 parts by weight of water, stirring at a high speed of 5000r/min, and removing NMP to obtain the waterborne polyurethane;
the attapulgite coated with the amino graphene is obtained by mixing an amino graphene solution with purified attapulgite and then drying the mixture, specifically, dissolving graphene oxide in NMP, adding ethylenediamine, wherein the weight ratio of the ethylenediamine to the graphene oxide is 1:12, stirring and reacting at 75 ℃ for 4.5 hours, and adding a reducing agent NaBH4Reducing agent NaBH4The weight ratio of the graphene oxide to the graphene oxide is 1.8:1, stirring and reacting for 4.5 hours at the temperature of 98 ℃, filtering and washing to obtain amino graphene; grinding attapulgite into powder, adding water to prepare an ore pulp solution with the concentration of 28 wt%, adding 1.6 wt% of sodium hexametaphosphate and 0.8 wt% of sodium hydroxide based on the attapulgite, ultrasonically stirring for 0.7h at 45 ℃, performing centrifugal separation, immersing the attapulgite into a sulfuric acid solution with the concentration of 6mol/L at 100 ℃ according to the solid-liquid weight ratio of 1:2.5 for 0.2h, performing suction filtration, drying, and calcining for 1.8h at 360 ℃ to obtain purified attapulgite; ultrasonically dispersing amino graphene in deionized water to obtain 0.3 wt% amino graphene solution, dropwise adding the amino graphene solution into purified attapulgite, wherein the volume-to-weight ratio of the graphene solution to the attapulgite is 4mL:10g, and drying at 80 ℃ to obtain the amino graphene coated attapulgite.
Example 5
A solid composite electrolyte comprising, in weight percent: 92% of waterborne polyurethane, 7% of lithium dioxalate borate and 1% of amino graphene-coated attapulgite. The preparation of the solid composite electrolyte into an electrolyte membrane comprises the following steps: mixing and stirring the water-containing polyurethane and the attapulgite coated with the amino graphene according to the weight percentage to obtain a polyurethane composite, adding lithium dioxalate borate into the polyurethane composite to obtain a lithium-doped polyurethane composite emulsion, and drying at 80 ℃ for 28 hours under a vacuum condition to obtain a solid composite electrolyte membrane;
the waterborne polyurethane is synthesized by the following method: 40 parts of poly (1, 6-hexanediol carbonate) glycol and 20 parts of 4,4' -dicyclohexylmethane diisocyanate in parts by weight are reacted for 3.5 hours at 75 ℃, 5 parts of dimethylolbutyric acid, 0.08 part of NMP and stannous octoate are added, the reaction is continued for 2.8 hours at 85 ℃, 5 parts of triethylamine is added for neutralization reaction after the temperature is reduced to 30 ℃, 220 parts of water is added, the high-speed stirring is carried out at the speed of 4000r/min, and the NMP is removed, so that the waterborne polyurethane is obtained;
the attapulgite coated with the amino graphene is obtained by mixing an amino graphene solution with purified attapulgite and then drying the mixture, specifically, dissolving graphene oxide in NMP, adding ethylenediamine, wherein the weight ratio of the ethylenediamine to the graphene oxide is 1:11, stirring and reacting at 80 ℃ for 3.5 hours, and adding a reducing agent NaBH4Reducing agent NaBH4The weight ratio of the graphene oxide to the graphene oxide is 1.6:1, stirring and reacting for 4.5 hours at the temperature of 98 ℃, filtering and washing to obtain amino graphene; grinding attapulgite into powder, adding water to prepare an ore pulp solution with the concentration of 29 wt%, adding 1.3 wt% of sodium hexametaphosphate and 0.9 wt% of sodium hydroxide based on the attapulgite, ultrasonically stirring for 0.5h at 50 ℃, performing centrifugal separation, immersing the attapulgite into a sulfuric acid solution with the concentration of 7mol/L at 105 ℃ according to the solid-liquid weight ratio of 1:1 for 0.5h, performing suction filtration, drying, and calcining for 1.2h at 380 ℃ to obtain purified attapulgite; ultrasonically dispersing amino graphene in deionized water to obtain 0.2 wt% amino graphene solution, dropwise adding the amino graphene solution into purified attapulgite, wherein the volume-to-weight ratio of the graphene solution to the attapulgite is 3mL:10g, and drying at 95 ℃ to obtain the amino graphene coated attapulgite.
The electrolyte membranes obtained in examples 1 to 5 described above were subjected to conductivity tests at different temperatures. The test method is an alternating current impedance method, alternating current impedance at the temperature of 25-100 ℃ is measured through an electrochemical workstation, the frequency range is from 100KHz to 0.01Hz, and the disturbance voltage is 10 mV; the conductivity results obtained by calculation using the formula σ ═ L/(R × S) are shown in table 1. Where σ is the ionic conductivity, L is the thickness of the electrolyte membrane, R is the resistance value of the electrolyte membrane, and S is the contact area of the electrolyte membrane and the stainless steel electrode. As can be seen from the data in Table 1, the electrolyte membranes obtained in examples 1-5 all reach a practical conductivity level below 100 ℃, and provide good application prospects for the preparation of lithium ion batteries.
Table 1 ion conductivities of electrolyte membranes prepared in examples 1 to 5 at different temperatures
Figure BDA0001863781310000111
Further, tensile strength tests were conducted on the electrolyte membranes obtained in examples 1 to 5 described above, and the results are shown in Table 2:
TABLE 2 tensile Strength Properties of electrolyte membranes prepared in examples 1-5
Figure BDA0001863781310000121
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical scope of the present invention, and equivalents and modifications thereof should be included in the technical scope of the present invention.

Claims (8)

1. The solid composite electrolyte is characterized by comprising the following raw materials in percentage by weight: 85-95% of waterborne polyurethane, 1-10% of lithium salt and 1-5% of amino graphene-coated attapulgite;
the amino graphene coated attapulgite is obtained by mixing an amino graphene solution with purified attapulgite and then drying the mixture;
the waterborne polyurethane comprises the following synthetic raw materials in parts by weight: 35-65 parts of aliphatic polycarbonate dihydric alcohol, 18-40 parts of diisocyanate, 2-8 parts of hydrophilic chain extender, 1-5 parts of triethylamine, 0.01-0.1 part of catalyst and 250 parts of water 150-;
the method for synthesizing the waterborne polyurethane comprises the following steps: carrying out prepolymerization reaction on aliphatic polycarbonate diol and diisocyanate, adding a hydrophilic chain extender, an organic solvent and a catalyst for continuous reaction, cooling, adding triethylamine for neutralization reaction, adding water, stirring at a high speed, and removing the organic solvent to obtain the waterborne polyurethane; wherein, the diisocyanate and the aliphatic polycarbonate dihydric alcohol are subjected to prepolymerization reaction according to the NCO/OH ratio of 1.5-2.0.
2. The solid-state composite electrolyte according to claim 1, wherein the amino graphene is an aminated modified graphene having an amino group on the surface.
3. The solid composite electrolyte according to claim 1 or 2, wherein the method of purifying attapulgite comprises: adding water into attapulgite powder to prepare an ore pulp solution, adding sodium hexametaphosphate and sodium hydroxide, ultrasonically stirring, centrifugally separating, immersing in a sulfuric acid solution, filtering, and calcining to obtain the purified attapulgite.
4. The solid composite electrolyte according to any one of claims 1 to 3, wherein the aliphatic polycarbonate diol is one or more of poly (1, 4-butylene carbonate) diol, poly (1, 5-pentanediol carbonate) diol, poly (1, 6-hexanediol carbonate) diol, or poly (1, 10-decanediol carbonate) diol; the diisocyanate is one or more of isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, 4 '-diphenylmethane diisocyanate or 4,4' -dicyclohexylmethane diisocyanate; the hydrophilic chain extender is dimethylolpropionic acid or dimethylolbutyric acid; the catalyst is one or more of stannous octoate, di-n-butyltin dilaurate, organic zinc or organic bismuth.
5. The solid composite electrolyte according to any one of claims 1 to 4, wherein the lithium salt is one or more of lithium perchlorate, lithium bistrifluoromethylsulfonyl imide, lithium bifluorosulfonimide, lithium hexafluorophosphate, lithium dioxalate borate, or lithium tetrafluoroborate.
6. A method for producing an electrolyte membrane according to the solid composite electrolyte of any one of claims 1 to 5, comprising: mixing and stirring water-based polyurethane and amino graphene-coated attapulgite to obtain a polyurethane composite, adding lithium salt into the polyurethane composite to obtain a lithium-doped polyurethane composite, and drying to form a film, thus obtaining the solid composite electrolyte film.
7. The method for producing an electrolyte membrane according to claim 6, wherein the drying to form a membrane includes: drying at 60-100 deg.C for 20-30 hr under vacuum.
8. Use of a solid composite electrolyte membrane prepared according to the method of claim 6 or 7 in a lithium battery.
CN201811346058.6A 2018-11-13 2018-11-13 Solid composite electrolyte and preparation method and application of electrolyte membrane thereof Active CN109585910B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811346058.6A CN109585910B (en) 2018-11-13 2018-11-13 Solid composite electrolyte and preparation method and application of electrolyte membrane thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811346058.6A CN109585910B (en) 2018-11-13 2018-11-13 Solid composite electrolyte and preparation method and application of electrolyte membrane thereof

Publications (2)

Publication Number Publication Date
CN109585910A CN109585910A (en) 2019-04-05
CN109585910B true CN109585910B (en) 2021-06-18

Family

ID=65922194

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811346058.6A Active CN109585910B (en) 2018-11-13 2018-11-13 Solid composite electrolyte and preparation method and application of electrolyte membrane thereof

Country Status (1)

Country Link
CN (1) CN109585910B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112421106A (en) * 2020-11-23 2021-02-26 浙江锋锂新能源科技有限公司 Composite film capable of prolonging cycle life of lithium battery and preparation method thereof

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103232584B (en) * 2013-04-23 2015-04-29 东莞长联新材料科技股份有限公司 High-performance environment-friendly type water-borne polyurethane and preparation method thereof
CN103357380A (en) * 2013-07-18 2013-10-23 江苏澳特邦非金属矿业有限公司 Preparation method of absorptive decolorant special for rapeseed oil refining
US10665841B2 (en) * 2013-11-05 2020-05-26 Murata Manufacturing Co., Ltd. Battery, separator, electrode, coating material, battery pack, electronic apparatus, electrically driven vehicle, electrical storage device, and electric power system
CN104852085A (en) * 2015-05-06 2015-08-19 深圳高远通新材料科技有限公司 Graphene polymer electrolyte and preparation method thereof
CN106549186B (en) * 2016-12-02 2019-03-05 中国科学院广州能源研究所 The preparation method of attapulgite hydridization polymethyl methacrylate lithium battery gel electrolyte
CN106711502B (en) * 2016-12-29 2019-09-06 中国科学院过程工程研究所 Inorganic composite nanoparticles, preparation method and the purposes in all-solid lithium-ion battery
CN107417872A (en) * 2017-07-24 2017-12-01 合肥思敬齐化工材料有限责任公司 A kind of preparation method of high crosslinking ultraviolet light solidfication water polyurethane
CN107799699B (en) * 2017-09-21 2020-06-30 中国科学院兰州化学物理研究所 Clay mineral composite lithium battery diaphragm and preparation method thereof
CN108075118A (en) * 2017-12-01 2018-05-25 江苏海四达电源股份有限公司 A kind of sulfur-based positive electrode material and preparation method thereof, lithium battery anode and lithium battery
CN108400380B (en) * 2018-04-24 2021-01-29 珠海冠宇电池股份有限公司 Preparation method of composite polymer electrolyte membrane and lithium ion battery

Also Published As

Publication number Publication date
CN109585910A (en) 2019-04-05

Similar Documents

Publication Publication Date Title
US10892521B2 (en) Solid polymer electrolyte based on modified cellulose and its use in lithium or sodium secondary batteries
Lin et al. Mechanically robust, nonflammable and surface cross-linking composite membranes with high wettability for dendrite-proof and high-safety lithium-ion batteries
WO2021012423A1 (en) Organic-inorganic composite solid electrolyte, preparation method therefor and use thereof
CN106785029B (en) Pluronic block copolymer-based hydrogel electrolyte and application thereof
CN106450445B (en) Based on fluorinated polyimide polymer dielectric and its preparation method and application
CN107317049A (en) A kind of single ion conductive polymer electrolyte and its production and use
Tseng et al. Lithium battery enhanced by the combination of in-situ generated poly (ionic liquid) systems and TiO2 nanoparticles
CN109585910B (en) Solid composite electrolyte and preparation method and application of electrolyte membrane thereof
US6544690B1 (en) Self-doped molecular composite battery electrolytes
CN110808358B (en) Polyurethane-protected metal cathode with rigid framework confinement function and preparation method thereof
CN108832178B (en) Single ion polymer electrolyte and preparation method and application thereof
KR101681297B1 (en) All solid lithium secondary batteries and method for manufacturing the same
Lu et al. Advanced strategies for solid electrolyte interface design with MOF materials
CN109585916B (en) Flame-retardant polymer solid electrolyte material, electrolyte membrane and application thereof
CN113506910A (en) Sodium ion composite solid electrolyte and preparation method thereof
CN111934005A (en) Crosslinked nanocellulose-based gel polymer electrolyte for lithium ion battery and preparation method and application thereof
Sharma et al. Role of additives for high performance polymer electrolytes
CN113363575B (en) Sulfonic polymer eutectic solid electrolyte and preparation method thereof
CN113363560B (en) Organic in-situ interface modified solid electrolyte and preparation method thereof
Eiamlamai Polymer electrolytes based on ionic liquids for lithium batteries
JP2007087737A (en) Lithium ion conductive material and lithium secondary battery
CN111029661A (en) Ultrathin flexible inorganic solid electrolyte of lithium battery, preparation method and application
Jaafar et al. Effect of graphene oxide on poly (methyl methacrylate)-grafted natural rubber polymer electrolytes
Dai et al. Zwitterionic liquid-based gel electrolyte for high performance lithium metal battery at low temperatures
CN113540559B (en) ZIF-8@ PEGMEM-co-AMPS-Li single ion polymer solid electrolyte and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant