CN107863555A - A kind of fire-retardant type solid polymer electrolyte and its application in solid secondary batteries - Google Patents
A kind of fire-retardant type solid polymer electrolyte and its application in solid secondary batteries Download PDFInfo
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- CN107863555A CN107863555A CN201711044195.XA CN201711044195A CN107863555A CN 107863555 A CN107863555 A CN 107863555A CN 201711044195 A CN201711044195 A CN 201711044195A CN 107863555 A CN107863555 A CN 107863555A
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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
- H01M2300/0085—Immobilising or gelification of electrolyte
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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
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Abstract
The invention discloses a kind of fire-retardant type solid polymer electrolyte, it is characterised in that including polyphosphate polymer and metal salt compound, the mass percent that wherein metal salt compound accounts for whole solid polymer electrolyte is 10 90%.The solid polymer electrolyte phosphorus content of the present invention it is high and also with methylphosphine structure, excellent fireproof performance, do not burn completely, good mechanical performance, ionic conductivity are high, electrochemical window is wider and electrode interface stability is good, especially suitable for high safety high-energy-density energy-storage battery, there is boundless application prospect in fields such as military affairs, Aero-Space, electric automobile and extensive energy-accumulating power stations.
Description
Technical field
The present invention relates to solid polymer electrolyte, in particular to a kind of fire-retardant type solid polymer electrolyte and its solid
Application in state secondary cell.
Background technology
The electrolyte of existing electrochemical energy storage cell such as lithium ion battery, mainly comprising liquid organic carbonate solvent, lithium
Salt and polyalkene diaphragm.Volatilization, and easy catching fire are easily revealed using substantial amounts of organic electrolyte, or even causes thing of exploding
Therefore it have impact on the security performance of battery.On the other hand, polyalkene diaphragm heat endurance is poor, when battery is heated or extreme
In the case of, it may occur that diaphragm retracts or thawing and cause battery short circuit, so as to which Fire explosion accident occur.Replaced with solid electrolyte
For the solid lithium battery of organic liquid electrolyte, the safety issue for thoroughly solving battery is expected to, meets following Large Copacity electricity
The demand of chemical energy storage technology development.Being divided to by solid electrolyte area type mainly includes two major classes：One kind is with organic polymer
The polymer solid lithium battery of electrolyte composition；Another kind of is the inorganic full-solid battery formed with inorganic solid electrolyte.
Traditional polyethylene glycol oxide (PEO)/lithium salts type electrolyte has been applied in all solid lithium polymer battery, but from
Still some problems need to solve from the point of view of practical angle：Linear and graft polymers mechanical performance is poor, is not easy to be made independent
The thin polymer film of support, and network polymers electrical conductivity is too small.Therefore this kind of electrolyte system is only suitable in high temperature or micro-
Worked under current condition, and practical application is obtained in the lithium battery for being difficult to work at normal temperatures.Makrolon is with gas dioxy
Change the environmental protective polymer that carbon is a kind of Wholly-degradable synthesized by raw material.Because it has light degradation and biological degradability, together
When also have excellent blocking oxygen and water performance, can be used as biodegradable engineering plastics, such as a sex medicine and food
Product packaging material, adhesive and composite etc..Compared with polyethylene glycol oxide, makrolon material is cheap, with lithium salts
With good compatibility, poly- glass transition temperature belongs to impalpable structure between 10~39.5 DEG C, and segment is easier to transport
It is dynamic.So makrolon/lithium salts type electrolyte has higher ionic conductivity and high lithium ion mobility coefficient at room temperature.
But the polymer such as high polymer material such as polyethylene glycol oxide and makrolon commonly used in solid polyelectrolyte
Electrolyte can burn in flame, thus can not ensure that extreme combustion explosion less occurs for its solid state battery made
Accident.Someone once studied polyphosphazene solid electrolyte, but because synthesis is complicated, the reason such as expensive also should without popularization
With.
Therefore, it is necessary to develop a kind of good flame retardation effect, electrical conductivity height, the solid polymer electrolyte of good mechanical performance
Matter.
The content of the invention
Present invention aim to solve the deficiency of above-mentioned background technology, there is provided a kind of good flame retardation effect, electrical conductivity be high,
The solid polymer electrolyte of good mechanical performance.
The technical scheme is that：A kind of fire-retardant type solid polymer electrolyte, it is characterised in that including polyphosphate
Polymer and metal salt compound, wherein metal salt compound mass percent are 10-90%, metal salt compound, polyphosphoric acid
Ester polymer mass percent sum is 100%；The metal salt compound is lithium salt compound or sodium salt compound；
The polyphosphate polymer is by methyl dichloro phosphine oxide and dihydric alcohol and/or trihydroxylic alcohol and/or tetrahydroxylic alcohol in system
Middle Cl/OH mol ratio is 1:1-1.2 when polymerization gained.
Polyphosphate constitutional unit is：
Preferably, wherein polyphosphate polymer is following I, II, III, IV or V structure：
Wherein, R1And R2For one kind and R in following structure1≠R2：
Wherein m=2-50, n=2-50, polyphosphate polymer molecular weight=100-15000.In formula III or IV, "~~
~~~~~~~~" represent that (all OH and Cl occur the dendritic structure that is formed with methyl dichloro phosphine oxide of trihydroxylic alcohol
Reaction), or the dendritic structure that trihydroxylic alcohol and/or dihydric alcohol and/or tetrahydroxylic alcohol are formed with methyl dichloro phosphine oxide is (all
OH and Cl all react), the structure can not be expressed with formula, thus with "~~~~~~~~~~" represent.Formula
In V, "~~~~~~~~~~" represent dendritic structure (all OH that tetrahydroxylic alcohol is formed with methyl dichloro phosphine oxide
All reacted with Cl), or the branch that trihydroxylic alcohol and/or dihydric alcohol and/or tetrahydroxylic alcohol are formed with methyl dichloro phosphine oxide
Shape structure (all OH and Cl react), the structure can not be expressed with formula, so with "~~~~~~~~~
~" represent.
Preferably, the polyphosphate polymer is by methyl dichloro phosphine oxide and dihydric alcohol and/or trihydroxylic alcohol and/or tetrahydroxylic alcohol
In N2The lower 50-80 DEG C of reaction 5-8h of protection is made.
Preferably, the dihydric alcohol is ethylene glycol, 1,3-PD, 1,2-PD, diglycol, two three second of contracting
One or more in glycol, tetraethylene-glycol, the trihydroxylic alcohol are trimethylolpropane, one kind in glycerine or two
Kind, the tetrahydroxylic alcohol is pentaerythrite.
Preferably, the lithium salt compound is di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, lithium perchlorate, hexafluorophosphoric acid
Lithium, hexafluoroarsenate lithium, LiBF4, trifluoromethyl sulfonic acid lithium, bis trifluoromethyl sulfimide lithium and double fluorine sulfimide lithiums
Among one or several kinds.
Preferably, wherein the sodium salt compound is double oxalic acid Boratexes, difluoro oxalate Boratex, sodium perchlorate, hexafluoro
Sodium phosphate, hexafluoroarsenate sodium, sodium tetrafluoroborate, trifluoromethyl sulfonate, bis trifluoromethyl sulfimide sodium and double fluorine sulphonyl are sub-
One or several kinds among amine sodium.Sodium salt combinations of materials structure is that the lithium in lithium salt compound is replaced with sodium, such as double
Oxalic acid Boratex structure is that the lithium in di-oxalate lithium borate is replaced with sodium；Bis trifluoromethyl sulfimide sodium structure is to be replaced with sodium
Lithium in double trifluoromethanesulfonimide lithiums；Double fluorine sulfimide sodium (molecular formula NaN (FSO2)2, structure is to replace LiFSI with sodium
In lithium.
Preferably, solid polymer electrolyte membrane thickness is 10-100 μm；Mechanical strength is 2-100MPa, and room-temperature ion is electric
Conductance is 1 × 10-5S/cm-5×10-3S/cm, electrochemical window are more than 3.5VLi+/ Li or 3.2VNa+/Na。
It is secondary in solid-state serondary lithium battery or solid-state that the present invention also provides a kind of above-mentioned fire-retardant type solid polymer electrolyte
Applied in sode cell.
Preferably, the solid-state serondary lithium battery includes positive pole, negative pole and fire-retardant type solid polymer electrolyte；It is described just
The active material of pole is cobalt acid lithium, LiFePO4, iron manganese phosphate for lithium, LiMn2O4, nickel ion doped, manganese cobalt nickel ternary material, sulphur, sulphur
One kind in compound, ferric sulfate lithium, lithium ion fluorophosphate, lithium vanadium fluorophosphate, lithium iron fluorophosphate, lithium manganese oxide；
The active material of the negative pole is lithium metal, lithium metal alloy, graphite, hard carbon, molybdenum disulfide, lithium titanate, graphene, oxidation
One kind in antimony, antimony carbon composite, tin antimony composite, Li-Ti oxide.
Preferably, the secondary sode cell of the solid-state includes positive pole, negative pole and fire-retardant type solid polymer electrolyte；It is described just
The active material of pole is vanadium phosphate sodium, sulfuric acid ferrisodium, sodium ion fluorophosphate, sodium vanadium fluorophosphate, sodium iron fluorophosphate, sodium manganese
One kind in oxide or sodium cobalt/cobalt oxide；The active material of negative pole is metallic sodium, hard carbon, molybdenum disulfide, sodium titanium oxide, nickel
Cobalt/cobalt oxide, antimony oxide, antimony carbon composite, tin antimony composite, para-phthalic sodium, Li-Ti oxide or sodium lithium titanyl
One kind in thing.
Beneficial effects of the present invention are：
Polyphosphate polymer has relatively low glass transition temperature and phosphor-containing flame-proof group, polyphosphate of the invention polymerization
Thing has relatively low glass transition temperature and phosphor-containing flame-proof group, and solid polymer electrolyte phosphorus content is high and has methylphosphine
Structure, excellent fireproof performance, do not burn completely, good mechanical performance, ionic conductivity are high, electrochemical window is wider and sector electrode
Face stability can be good, especially suitable for high safety high-energy-density energy-storage battery, in military affairs, Aero-Space, electric automobile and greatly
The fields such as scale energy-accumulating power station have boundless application prospect.
Brief description of the drawings
Fig. 1 is the infrared spectrogram that polyphosphate is made in embodiment 1
Fig. 2 is the DSC test charts that polyphosphate is made in embodiment 1
Embodiment
The present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings.
Part I prepares polyphosphate polymer
Embodiment 1
Poly- methylphosphonic acid diglycol ester：In the 100mL three-necked flasks equipped with spherical condensation tube, 0.1mol is put into
(10.6g) diglycol, and in room temperature N2Under conditions of protection, 0.1mol (13.3g) dichloromethyl phosphine is taken with syringe
(about 0.5h) is slowly dropped into there-necked flask, is warming up to after being added dropwise to complete at 50 DEG C and is incubated 1h, 2h is incubated at 60 DEG C, is incubated at 70 DEG C
2h, 1h is incubated at 80 DEG C, faint yellow solid is obtained after cooling.
Resulting polymers concrete structure formula is：
Embodiment 2
Poly- methylphosphonic acid Triethylene Glycol：In the 100mL three-necked flasks equipped with spherical condensation tube, 0.1mol is put into
(15.0g) triethylene-glycol, and in room temperature N2Under conditions of protection, 0.1mol (13.3g) dichloromethyl phosphine is taken with syringe
(about 0.5h) is slowly dropped into there-necked flask, is warming up to after being added dropwise to complete at 50 DEG C and is incubated 1h, 2h is incubated at 60 DEG C, is incubated at 70 DEG C
2h, after being incubated 1h at 80 DEG C, cooling obtains faint yellow solid.
Resulting polymers concrete structure formula is
Embodiment 3
Poly- methylphosphonic acid trihydroxymethylpropanyl ester：In the 100mL three-necked flasks equipped with spherical condensation tube, it is put into
0.12mol (16.08g) trimethylolpropane, and in 60 DEG C of meltings, N2Under conditions of protection, 0.18mol is drawn with syringe
(23.94g) dichloromethyl phosphine is slowly dropped into there-necked flask (about 1h), is incubated 1h at 60 DEG C after being added dropwise to complete, 5h is incubated at 70 DEG C,
The faint yellow solid obtained after cooling.
Resulting polymers concrete structure formula is：
Embodiment 4
Poly- methylphosphonic acid (pentaerythrite-diglycol) ester：In the 100mL three-necked flasks equipped with spherical condensation tube
In, 0.025mol (3.4g) pentaerythrites and 0.05mol (5.3g) diglycol are put into, and in 60 DEG C of meltings, N2Protection
Under conditions of, draw 0.10mol (13.3g) dichloromethyl phosphine with syringe and be slowly dropped into there-necked flask (about 1h), be added dropwise to complete
1h is incubated at 60 DEG C afterwards, and 5h, the faint yellow solid obtained after cooling are incubated at 70 DEG C.
Resulting polymers concrete structure formula is：
Embodiment 5
Poly- methylphosphonic acid (pentaerythrite-triethylene-glycol) ester：In the 100mL three-necked flasks equipped with spherical condensation tube
In, 0.025mol (3.4g) pentaerythrites and triethylene-glycol 0.05mol (7.5g) are put into, and in 60 DEG C of meltings, N2Protection
Under conditions of, draw 0.10mol (13.3g) dichloromethyl phosphine with syringe and be slowly dropped into there-necked flask (about 1h), be added dropwise to complete
1h is incubated at 60 DEG C afterwards, and 5h, the faint yellow solid obtained after cooling are incubated at 70 DEG C.
Resulting polymers concrete structure formula is：
Embodiment 6
Poly- methylphosphonic acid (trimethylolpropane-diglycol) ester：In tri- mouthfuls of burnings of 100mL equipped with spherical condensation tube
In bottle, 0.04mol (5.36g) trimethylolpropanes and diglycol 0.04mol (4.24g) are put into, and is melted in 60 DEG C,
N2Under conditions of protection, draw 0.10mol (13.3g) dichloromethyl phosphine with syringe and be slowly dropped into there-necked flask (about 1h), drip
1h is incubated after the completion of adding at 60 DEG C, 5h, the faint yellow solid obtained after cooling are incubated at 70 DEG C.
Resulting polymers concrete structure formula is：
Embodiment 7
Poly- methylphosphonic acid (diglycol-triethylene-glycol) ester：In tri- mouthfuls of burnings of 100mL equipped with spherical condensation tube
In bottle, 0.07mol (5.3g) diglycols and 0.05mol (7.5g) triethylene-glycol are put into, and in room temperature N2Protection
Under conditions of, take 0.1mol (13.3g) dichloromethyl phosphine to be slowly dropped into there-necked flask (about 0.5h) with syringe, after being added dropwise to complete
60 DEG C of insulation 2h are warming up to, 70 DEG C of insulation 3h, faint yellow solid are obtained after cooling.
Resulting polymers concrete structure formula is：
Embodiment 8
Poly- methylphosphonic acid pentaerythrite：In the 100mL three-necked flasks equipped with spherical condensation tube, 0.055mol is put into
(7.5g) pentaerythrite, and in 60 DEG C of meltings, N2Under conditions of protection, 0.10mol (13.3g) dichloromethyl is drawn with syringe
Phosphine is slowly dropped into there-necked flask (about 1h), and 60 DEG C of insulation 2h after being added dropwise to complete, 70 DEG C are incubated 5h, the pale yellow colored solid obtained after cooling
Body.
Resulting polymers concrete structure formula is：
Part II prepares fire-retardant type solid polymer electrolyte
Embodiment 9
The poly- methylphosphonic acid trihydroxymethylpropanyl esters of 1g, 20g tetrahydrofurans in embodiment 3 is added to 100ml flask
In, 6h is then stirred at normal temperatures, obtains homogeneous polymer solution.Then it is under argon gas protection, the double fluorine sulphonyl of 0.25g are sub-
Amine lithium, it is added among above-mentioned homogeneous solution, stirs 6h at normal temperatures, get a uniform mixture.Solution is uniformly poured into a mould
Film forming obtains all solid state electrolyte.
Embodiment 10
The poly- methylphosphonic acids of 1g (trimethylolpropane-diglycol) ester, 20g tetrahydrofurans in embodiment 6 is added
Enter into 100ml flask, then stir 6h at normal temperatures, obtain homogeneous polymer solution.Then, will under argon gas protection
The double fluorine Lithium bis (oxalate) borates (LiDFOB) of 0.28g, are added among above-mentioned homogeneous solution, stir 6h at normal temperatures, obtain uniformly
Mixed solution.Solution is uniformly poured into a mould to film forming and obtains all solid state electrolyte.
Embodiment 11
By the poly- methylphosphonic acids of 1g (trimethylolpropane-diglycol) ester, the 20gN in embodiment 6, N- dimethyl
Formamide is added in 100ml flask, then stirs 6h at normal temperatures, obtains homogeneous polymer solution.Then in argon gas
Under protection, 0.28g difluorine oxalic acid boracic acid lithiums, 0.3g hexafluoroarsenate lithiums are added among above-mentioned homogeneous solution, at normal temperatures
6h is stirred, is got a uniform mixture.Solution is uniformly poured into a mould to film forming and obtains all solid state electrolyte.
Embodiment 12
By the poly- methylphosphonic acid diglycol esters of 0.1g, the 20gN in embodiment 1, dinethylformamide is added to
In 100ml flask, 6h is then stirred at normal temperatures, obtains homogeneous polymer solution.Then, will under argon gas protection
0.45g trifluoromethyl sulfonates, 0.45g sodium tetrafluoroborates are added among above-mentioned homogeneous solution, stir 6h at normal temperatures, obtain
To homogeneous mixture solotion.Solution is uniformly poured into a mould to film forming and obtains all solid state electrolyte.
Embodiment 13
By the poly- methylphosphonic acid Triethylene Glycols of 0.9g, the 20gN in embodiment 2, dinethylformamide is added to
In 100ml flask, 6h is then stirred at normal temperatures, obtains homogeneous polymer solution.Then under argon gas protection, by 0.1g
Hexafluoroarsenate sodium, it is added among above-mentioned homogeneous solution, stirs 6h at normal temperatures, get a uniform mixture.Solution is equal
Even cast film forming obtains all solid state electrolyte.
All solid state electrolyte obtained by embodiment 9-13 is coordinated with positive pole, negative pole and is assembled into fire-retardant type solid state battery, solid-state
Serondary lithium battery includes positive pole, negative pole and the polyphosphate polymer dielectric being placed between positive pole and negative pole；The activity of positive pole
Material be cobalt acid lithium, LiFePO4, iron manganese phosphate for lithium, LiMn2O4, nickel ion doped, manganese cobalt nickel ternary material, sulphur, sulfur compound,
One kind in ferric sulfate lithium, lithium ion fluorophosphate, lithium vanadium fluorophosphate, lithium iron fluorophosphate, lithium manganese oxide；The negative pole
Active material be lithium metal, lithium metal alloy, graphite, hard carbon, molybdenum disulfide, lithium titanate, graphene, antimony oxide, antimony carbon answers
One kind in condensation material, tin antimony composite, Li-Ti oxide.
The secondary sode cell of solid-state includes positive pole, negative pole and the polyphosphate polymer electrolytic being placed between positive pole and negative pole
Matter；The active material of positive pole is vanadium phosphate sodium, sulfuric acid ferrisodium, sodium ion fluorophosphate, sodium vanadium fluorophosphate, sodium iron fluorophosphoric acid
One kind in salt, sodium manganese oxide or sodium cobalt/cobalt oxide；The active material of negative pole is metallic sodium, hard carbon, molybdenum disulfide, sodium titanyl
Compound, nickel cobalt oxide, antimony oxide, antimony carbon composite, tin antimony composite, para-phthalic sodium, Li-Ti oxide or sodium
One kind in Li-Ti oxide.
The performance test of all solid state electrolyte is made in Part III
The infrared spectrogram of polyphosphate is made for embodiment 1 as shown in figure 1, hydroxyl participates in instead substantially as can be seen from Figure 1
Answer, generate the polyphosphate polymer of target.
The DSC test charts of polyphosphate are made as shown in Fig. 2 can obtain glass transition temperature from Fig. 2 as -58 in embodiment 1
DEG C, low glass transition temperature is advantageous to lithium ion transport.
The fire resistance that polyphosphate is made in embodiment 1-8 is as shown in table 1.
Electrolyte performance is characterized：
Film thickness：Using the thickness of micrometer (0.01 millimeter of precision) test all solid state electrolyte, 5 on sample are arbitrarily taken
It is individual, and average.
Ionic conductivity：Electrolyte is clamped with two panels stainless steel, is placed in 2032 type battery cases.Sodium ion electrical conductivity uses
Electrochemical alternate impedance spectrum measures, using formula：σ=L/ARb, wherein, L is the thickness of electrolyte, and A is stainless steel substrates room temperature
Area, RbTo measure the impedance drawn.
Electrochemical window：Electrolyte is clamped with stainless steel substrates and sodium piece, is placed in 2032 type battery cases.Electrochemical window with
Electrochemical workstation carries out linear voltammetric scan measurement, take-off potential 2.5V, maximum potential 5.5V, sweep speed 1mV/
s.(referring to table 2).
Acquired results are listed in table 2.From the results shown in Table 2, it is entirely solid using organo-mineral complexing provided by the invention
The mechanical strength of state electrolyte is taller and bigger in 1MPa；Ionic conductivity scope is 1 × 10 at room temperature-5S/cm-5×10-3S/cm,
Can be with high rate charge-discharge；Electrochemical window is more than 3.5V.
Polyphosphate fire resistance test result is made in the embodiment 1-8 of table 1
The embodiment 9-13 test results of table 2
Claims (10)
- A kind of 1. fire-retardant type solid polymer electrolyte, it is characterised in that including polyphosphate polymer and metal salt compound, Wherein metal salt compound mass percent is 10-90%, metal salt compound, polyphosphate polymer quality percentage sum For 100%；The metal salt compound is lithium salt compound or sodium salt compound；The polyphosphate polymer is by methyl dichloro phosphine oxide and dihydric alcohol and/or trihydroxylic alcohol and/or the tetrahydroxylic alcohol Cl/ in system OH mol ratio is 1:1-1.2 when polymerization gained.
- 2. fire-retardant type solid polymer electrolyte as claimed in claim 1, it is characterised in that wherein polyphosphate polymer is I, II, III, IV or V structure below：Wherein, R1And R2For one kind and R in following structure1≠R2：Wherein m=2-50, n=2-50, polyphosphate polymer molecular weight=100-15000.
- 3. fire-retardant type solid polymer electrolyte as claimed in claim 1, it is characterised in that the polyphosphate polymer by Methyl dichloro phosphine oxide is with dihydric alcohol and/or trihydroxylic alcohol and/or tetrahydroxylic alcohol in N2The lower 50-80 DEG C of reaction 5-8h of protection is made.
- 4. fire-retardant type solid polymer electrolyte as claimed in claim 1, it is characterised in that the dihydric alcohol be ethylene glycol, One or more in 1,3-PD, 1,2-PD, diglycol, triethylene-glycol, tetraethylene-glycol, institute Trihydroxylic alcohol is stated as one or both of trimethylolpropane, glycerine, the tetrahydroxylic alcohol is pentaerythrite.
- 5. fire-retardant type solid polymer electrolyte as claimed in claim 1, it is characterised in that the lithium salt compound is double grass Sour lithium borate, difluorine oxalic acid boracic acid lithium, lithium perchlorate, lithium hexafluoro phosphate, hexafluoroarsenate lithium, LiBF4, trifluoromethyl sulphur One or several kinds among sour lithium, bis trifluoromethyl sulfimide lithium and double fluorine sulfimide lithiums.
- 6. fire-retardant type solid polymer electrolyte as claimed in claim 1, it is characterised in that the sodium salt compound is double grass Sour Boratex, difluoro oxalate Boratex, sodium perchlorate, sodium hexafluoro phosphate, hexafluoroarsenate sodium, sodium tetrafluoroborate, trifluoromethyl sulphur One or several kinds among sour sodium, bis trifluoromethyl sulfimide sodium and double fluorine sulfimide sodium.
- 7. fire-retardant type solid polymer electrolyte as claimed in claim 1, it is characterised in that solid polymer electrolyte membrane is thick Spend for 10-100 μm；Mechanical strength is 2-100MPa, and conductivity at room temperature is 1 × 10-5S/cm-5×10-3S/cm, electrochemistry Window is more than 3.5VLi+/ Li or 3.2VNa+/Na。
- 8. a kind of fire-retardant type solid polymer electrolyte as claimed in claim 1 is in solid-state serondary lithium battery or the secondary sodium of solid-state Applied in battery.
- 9. fire-retardant type solid polymer electrolyte as claimed in claim 8 is in solid-state serondary lithium battery or the secondary sode cell of solid-state Middle application, it is characterised in that the solid-state serondary lithium battery includes positive pole, negative pole, fire-retardant type solid polymer electrolyte；It is described The active material of positive pole be cobalt acid lithium, LiFePO4, iron manganese phosphate for lithium, LiMn2O4, nickel ion doped, manganese cobalt nickel ternary material, sulphur, One in sulfur compound, ferric sulfate lithium, lithium ion fluorophosphate, lithium vanadium fluorophosphate, lithium iron fluorophosphate, lithium manganese oxide Kind；The active material of the negative pole is lithium metal, lithium metal alloy, graphite, hard carbon, molybdenum disulfide, lithium titanate, graphene, oxygen Change one kind in antimony, antimony carbon composite, tin antimony composite, Li-Ti oxide.
- 10. fire-retardant type solid polymer electrolyte as claimed in claim 8 is in solid-state serondary lithium battery or the secondary sodium electricity of solid-state Applied in pond, it is characterised in that the secondary sode cell of solid-state includes positive pole, negative pole, fire-retardant type solid polymer electrolyte；Institute The active material for stating positive pole is vanadium phosphate sodium, sulfuric acid ferrisodium, sodium ion fluorophosphate, sodium vanadium fluorophosphate, sodium iron fluorophosphate, One kind in sodium manganese oxide or sodium cobalt/cobalt oxide；The active material of negative pole is metallic sodium, hard carbon, molybdenum disulfide, sodium titanyl Thing, nickel cobalt oxide, antimony oxide, antimony carbon composite, tin antimony composite, para-phthalic sodium, Li-Ti oxide or sodium lithium One kind in titanium oxide.
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| US11289736B2 (en) | 2019-06-25 | 2022-03-29 | Robert Bosch Gmbh | Polymer electrolyte material for lithium battery cells |
| CN112126068B (en) * | 2019-06-25 | 2022-10-04 | 罗伯特·博世有限公司 | Polymer electrolyte material for lithium battery cells |
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