CN104183868A - Preparation method of perfluoro sulfonyl bis-nitrile amine lithium polymer electrolyte and lithium-sulfur secondary battery - Google Patents
Preparation method of perfluoro sulfonyl bis-nitrile amine lithium polymer electrolyte and lithium-sulfur secondary battery Download PDFInfo
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- CN104183868A CN104183868A CN201410400586.0A CN201410400586A CN104183868A CN 104183868 A CN104183868 A CN 104183868A CN 201410400586 A CN201410400586 A CN 201410400586A CN 104183868 A CN104183868 A CN 104183868A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of perfluoro sulfonyl bis-nitrile amine lithium polymer electrolyte. The preparation method comprises the following steps: enabling malononitrile and lithium hydride to be subjected to hybrid reaction in specific mixed solution A at proper temperature in an inert atmosphere for not less than 5h to obtain lithium malononitrile solution; carrying out similar-conversion reaction on the purified lithium malononitrile solution and perfluoro sulfonyl resin with an ethyoxyl side chain, wherein excessive lithium malononitrile solution is used, performing post-processing treatment after reaction to obtain the perfluoro sulfonyl bis-nitrile amine lithium polymer electrolyte with a side chain containing bis-nitrile amine lithium group. A lithium-sulfur secondary battery comprises a lithium cathode, an anode piece, an electrolyte membrane and organic electrolyte; electrolyte used by the electrolyte membrane is perfluoro sulfonyl bis-nitrile amine lithium polymer electrolyte; the anode piece is mainly composed of a current collector and a sulfur anode active material; and the organic electrolyte contains lithium salt and non-aqueous solvent. The lithium-sulfur secondary battery has high gram volume of the active substance in a charging and discharging process, low dissolving loss of the active substance and long cycle life.
Description
Technical field
The preparation and the corresponding lithium-sulfur cell making that the present invention relates to a kind of functional electrolyte film, relate in particular to a kind of perfluor sulfonyl dicyanamide lighium polymer electrolyte preparation method and lithium-sulfur rechargeable battery thereof.
Background technology
Fast development along with current communication, portable electric appts, electric automobile and space science and technology etc., has proposed more and more higher requirement to the performance of energy-storage battery, and development high-energy-density, low cost and eco-friendly Novel lithium storage battery have great importance.
Lithium-sulfur rechargeable battery based on lithium an-ode and sulphur positive pole is one of combination that in known chemical bilateral system, energy density is the highest.The theoretical energy density of lithium sulfur system is 2600Wh/kg, can expect that the actual energy density realizing is 700Wh/kg, is 3 times of existing lithium ion battery.Although the attainable energy density of lithium-sulfur cell has reached 300～400Wh/kg at present, but sulphur positive pole is non-conductive, electrochemical reaction process is complicated, cathode of lithium activity is high, the poly-sulphur lithium of lithium-sulfur cell charge and discharge process intermediate product is dissolved in electrolyte, in liquid phase, via porous septum, diffuse to negative pole (" flying shuttle effect " occurs), cause the consumption of positive active material and the Corrosion and passivation of negative pole, the cycle performance of lithium-sulfur cell is caused and had a strong impact on.
Existing perfluor sulfonyl dicyanamide lighium polymer electrolyte can overcome above-mentioned defect to a certain extent, but existing preparation technology's yield is lower, and cost is high, is difficult to be applied to suitability for industrialized production.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, provide a kind of and stop that anion and organic molecule see through, have higher ionic conductivity and the higher perfluor sulfonyl dicyanamide lighium polymer electrolyte preparation method of chemistry, electrochemical stability and yield, also provide a kind of charge and discharge process active material gram volume compared with the molten mistake of high, active material less, the lithium-sulfur rechargeable battery that has extended cycle life.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of perfluor sulfonyl dicyanamide lighium polymer electrolyte preparation method with higher yields (polymer yield can reach more than 90%), comprises the following steps:
(1) by malononitrile and lithium hydride under specific blend solvent orange 2 A exists under proper temperature and inert atmosphere hybrid reaction, reaction time is no less than 5h, remove by filter after completion of the reaction unreacted raw material and precipitation accessory substance etc., can prepare malononitrile lithium solution;
(2) be there is to similar transformation reaction to the perfluor sulfonyl fluororesin with ethyoxyl side chain in the above-mentioned malononitrile lithium solution after purifying, that malononitrile lithium keeps is excessive (malononitrile lithium and the preferred ratio range of perfluor sulfonyl fluororesin are controlled at 5: 1～2: 1), reacted by subsequent treatment, obtained side chain containing the perfluor sulfonyl dicyanamide lighium polymer electrolyte of dicyanamide lithium group.
The technical scheme of the invention described above mainly breaks through from 2, to realize the remarkable lifting of product yield: be first from the choice and optimization of reaction dissolvent, by selecting a kind of specific mixed solvent to improve the yield of product, this is the important improvement that inventor determines after repetition test and creative work; In addition, the present invention also guarantees the yield of product by extending the reaction time, and the defined reaction time is no less than 5h, can realize and having complementary advantages with the choice and optimization of aforementioned mixed solvent, greatly to improve the yield of product of the present invention by extending the reaction time.
Above-mentioned preparation method, preferably, in described step (1), according to the requirement of stoichiometric proportion, lithium hydride reacts with 2:1 equivalent with malononitrile, but because lithium hydride is active higher reactant, easily there is side reaction, therefore reaction system is except carrying out purified treatment, also should preferably control lithium hydride should be excessive, excessive ratio is 1%～80% (the excessive ratio of lithium hydride is the mass fraction of the reasonable opinion of excessive part consumption), be beneficial to malononitrile and replace completely, and subsequent reactions obtains higher polymer yield.
Above-mentioned preparation method, preferred, in described step (1), the actual conditions of hybrid reaction for to react 5h～40h under 20 ℃～100 ℃ return stirring conditions.Need to benly be, it is very important to improving the yield of polymer that reaction time is controlled at 5h above, this is also one of emphasis feature of the present invention, this is mainly the following research based on us: the methylene in malononitrile molecule contains two reactive hydrogens, lithium hydride and its generation electrophilic substitution reaction, produce hydrogen; A small amount of impurity in raw material and a substitution reaction of methylene have reaction rate faster, and releasing hydrogen gas, produces a large amount of bubbles, if but fully replace reaction time that need to be longer; If substitution reaction is insufficient, will cause end-product because solubility reduces productive rate, affect the performance of dielectric film simultaneously.
Above-mentioned preparation method, preferably, in described step (1), described specific blend solvent orange 2 A is the mixed system of methyl phenyl ethers anisole and 1-METHYLPYRROLIDONE, and the mass ratio of methyl phenyl ethers anisole and 1-METHYLPYRROLIDONE is 20: 1～2: 1, the addition of described specific blend solvent orange 2 A is 10～50 times of malononitrile quality.In the present invention, we are by carrying out repetition test and allotment to tens kinds of solvents, final discovery methyl phenyl ethers anisole has appropriate dissolubility with the mixed solvent of 1-METHYLPYRROLIDONE to the intermediate product reacting and end-product, this is conducive to keep in course of reaction the homogeneous reaction of suitable degree, further improves productive rate.This characteristic, when selecting other single solvents or other combination solvents, is difficult to see.
Above-mentioned preparation method, preferred, in described step (2), the actual conditions of similar transformation reaction is stirring and refluxing reaction 4h～30h under the inert atmosphere of 40 ℃～120 ℃.
Above-mentioned preparation method, preferably, in described step (2), subsequent treatment refers to (preferably carries out filtering and washing with the mixed solvent containing ethanol, water etc.) by the polymer precipitation of described similar transformation reaction generation after filtering and washing, dry weighing calculated thick productive rate, or directly add solvent B stirring and dissolving at 30 ℃～100 ℃, then a small amount of insoluble matter of filtering obtains perfluor sulfonyl dicyanamide lighium polymer electrolyte solution (clear solution); Through distillation and concentration, obtain perfluor sulfonyl dicyanamide lighium polymer electrolyte concentrate again; General preferred is 10%～30% by solution distillation and concentration to concentration.After insoluble matter washing is dry, weigh, for calculating the electrolytical actual yield of perfluor sulfonyl dicyanamide lighium polymer.
Above-mentioned preparation method, preferably, described subsequent treatment also comprises: by coating machine coating for the polymer dielectric concentrate making, blade coating device blade coating film forming or casting film-forming, after just doing, add extractant, solution extraction is out made to polymer two-step film forming, after vacuumize, 120 ℃～200 ℃ heat treatment 0.5h～4h, obtain perfluor sulfonyl dicyanamide lighium polymer dielectric film after cooling; Selected extractant is at least one in ethanol, isopropyl alcohol, ether, propyl ether, oxolane, ethylene carbonate, propene carbonate, diethyl carbonate, methyl ethyl carbonate, dioxolane, water, carrene, dichloroethanes, toluene, dimethylbenzene.Extractant add the removal completely that is conducive to dielectric film volatile matter, be also conducive to the electrolyte demoulding simultaneously.
Above-mentioned preparation method, preferred, described solvent B is one or both the mixing in methyl phenyl ethers anisole, 1-METHYLPYRROLIDONE, N-ethyl pyrrolidone, dichloroethanes, dimethyl sulfoxide (DMSO), sulfolane, water, triglyme, tetraethylene glycol dimethyl ether etc.
Above-mentioned preparation method, preferred, described specific blend solvent orange 2 A can be identical with the part composition of solvent B, and solvent orange 2 A and solvent B be the mixed solvent system that comprises methyl phenyl ethers anisole, makes solids content wherein reach 4%～50% after adding solvent B.In above-mentioned two-step reaction, the troublesome operation of using identical dicyandiamide solution can avoid solvent removal to process, reduces loss and the concentrated side reaction that may bring of high temperature distillation of product in subsequent processes.In addition, the mixed solvent system that comprises one or both ether materials and other kind solvent, can adapt in above-mentioned two-step reaction and improve reaction temperature and the requirement that reduces solvent evaporates amount, is easy to realize the two-step reaction purifying of principal product separately.
The preparation method of the invention described above mainly adopts the similar transformation method of polymer, makes to take the electrolyte that carbon-chain structure that perfluor replaces contains sulphonyl dicyanamide lithium group as main chain, ethyoxyl side chain terminal; This system is by the crystalline texture of main chain densification, and in the charge effect of side chain and bulk effect inhibition electrolyte, the migration of anion and organic solvent molecule sees through, thereby obtains single cation transport.
As a total technical conceive, the present invention also provides a kind of lithium-sulfur rechargeable battery, comprises cathode of lithium, anode pole piece, dielectric film, organic electrolyte;
The electrolyte that described dielectric film is used is the perfluor sulfonyl dicyanamide lighium polymer electrolyte that the invention described above preparation method obtains;
Described cathode of lithium mainly comprises the negative active core-shell material (also can comprise electric conducting material and bonding agent etc.) that lithium metal or lithium alloys form;
Described anode pole piece is mainly comprised of the collector (being preferably aluminium foil or aluminium net) of conduction current and the positive electrode active materials, conductive agent and the adhesive that are coated on collector; Described positive electrode active materials is at least one in sulphur simple substance, organic sulfur compound, carbon sulphur polymer; Described conductive agent is carbon-based conductive agent, as one or more in preferred conductive carbon black, acetylene black or graphite powder; Described adhesive is preferably polyoxygenated ethane, butadiene-styrene rubber, Kynoar or Kynoar-hexafluoropropylene copolymer etc.Wherein, the mass percent of positive electrode active materials, conductive agent and adhesive is preferably respectively 50%～80%, 15%～30% and 5%～20%.
Described organic electrolyte comprises lithium salts and nonaqueous solvents, and described lithium salts is selected from lithium hexafluoro phosphate (LiPF
6), LiBF4 (LiBF
4), hexafluoroarsenate lithium (LiAsF
6), lithium perchlorate (LiClO
4), lithium trifluoromethanesulp,onylimide (LiN (CF
3sO
2)
2), trifluoromethyl sulfonic acid lithium (LiSO
3cF
3), at least one in the poly-sulphur lithium of lithium nitrate, different valence state, described nonaqueous solvents comprises acetonitrile, cyclohexane, cyclohexanone, isopropyl alcohol, oxolane, 2-methyltetrahydrofuran, ethylene carbonate, propene carbonate, butylene, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, methyl formate, Ethyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, dimethoxy-ethane, 1, 3-dioxolane, diethylene glycol dimethyl ether (dimethoxy-ethyl ether), triglyme, tetraethylene glycol dimethyl ether, glycol dimethyl ether, sulfolane, two methylene sulfones, at least one in dimethyl sulfone.The nonaqueous solvents adding has certain activation to dielectric film, nonaqueous solvents in dielectric film meeting Electolyte-absorptive, reach after certain balance, with higher ionic conductivity, in lithium-sulfur rechargeable battery, bring into play good conductive lithium ion and suppress anion and the mutual diffusion mobility of organic molecule between both positive and negative polarity.The kind of solvent has a certain impact to the conductivity of dielectric film, by regulating kind, the concentration of nonaqueous solvents in organic electrolyte, can regulate within the specific limits the ionic conduction characteristic of dielectric film, and improve the cycle performance of lithium-sulfur rechargeable battery.
Compared with prior art, the invention has the advantages that:
1. the perfluor sulfonyl dicyanamide lighium polymer electrolyte that the invention described above preparation method makes, its main chain highly crystalline forms fine and close barrier layer, and side chain has anion fixed charge, jointly stops that anion and organic molecule see through.This polymer dielectric main chain is the carbon carbon bond that perfluor replaces, and the fixing anion of side chain is the sulphonyl dicyanamide anion with larger volume, has higher ionic conductivity and chemistry, electrochemical stability.
2. to adopt perfluor sulfonyl fluororesin be raw material to preparation method of the present invention, prepare by similar transformation reaction to malononitrile lithium, the product mixtures that adopts synthesis step of the present invention and process conditions to prepare, its purification process can be filtered after stirring and dissolving at room temperature～100 ℃, obtain the higher polymer solution of purity, whole preparation process is simple, and product polymer yield is high, and the single lithium ion polymer yield finally making is higher than 90%.
3. the functional polymer dielectric film that lithium-sulfur rechargeable battery of the present invention mainly makes by the present invention suppresses poly-sulphur anion, alcoxyl anion and organic solvent be phase counterdiffusion between both positive and negative polarity, in lithium-sulfur rechargeable battery, show as and stop poly-sulphur anion, alcoxyl anion etc. in electrolyte, spread and with lithium an-ode generation side reaction, and there is higher ionic conductivity, thereby guarantee the higher gram volume of battery charge and discharge process active material performance, reduce the molten mistake of active material simultaneously, improve the cycle life (circulating 100 Capacitance reserves more than 80%) of lithium-sulfur rechargeable battery.
Generally speaking, step of preparation process of the present invention is simple, excellent product performance, and product yield is higher, can be advantageously applied in industrial practice.
Accompanying drawing explanation
Fig. 1 is single lithium ion polymer electrolyte film sample of the embodiment of the present invention 1 preparation.
Fig. 2 is the fluorine nuclear magnetic spectrum of single lithium ion polymer of the embodiment of the present invention 1 preparation.
Fig. 3 is the cycle performance curve that adopts the lithium-sulfur cell of polymer dielectric film in the embodiment of the present invention 1.
Fig. 4 is 0.1C charge/discharge capacity and the internal drag curve that adopts the lithium-sulfur cell of polymer dielectric film in the embodiment of the present invention 2.
Embodiment
For the ease of understanding the present invention, below in connection with preferred embodiment, the present invention is done more comprehensively, described meticulously, but protection scope of the present invention is not limited to following specific embodiment.
Unless otherwise defined, all technical terms of hereinafter using are identical with the implication that those skilled in the art understand conventionally.Technical term used herein, just in order to describe the object of specific embodiment, is not to be intended to limit the scope of the invention.
Apart from special instruction, various reagent, the raw material of using in the present invention is the commodity that can buy from the market or the product that can make by known method.
Embodiment 1:
A perfluor sulfonyl dicyanamide lighium polymer electrolyte preparation method of the present invention, comprises the following steps:
(1) 1.69g the third two eyeballs are dissolved in the mixed solvent that 20g methyl phenyl ethers anisole and 5gN-methyl pyrrolidone form, then splash in the 250ml single port flask that 0.71g lithium hydride is housed, under nitrogen atmosphere, 30 ℃ of return stirrings reaction 5 hours, make the mixed solution containing malononitrile lithium, remove by filter unreacted raw material lithium hydride and precipitation accessory substance etc., obtain the malononitrile lithium solution of light red clear.
(2) in the above-mentioned malononitrile lithium solution after purifying, add 25g with the perfluor sulfonyl fluororesin of ethyoxyl side chain, the ion exchange capacity of perfluor sulfonyl fluororesin used is 0.91mmol/100g, under nitrogen atmosphere, 70 ℃ of stirring and refluxing reaction 15 hours, obtain side chain containing the electrolytical solution of perfluor sulfonyl dicyanamide lighium polymer of dicyanamide lithium group.
(3) solution system obtaining after similar transformation reaction in step (2) is carried out to suction filtration and obtain solid polymer crude product, solid polymer is dry after the mixed solvent filtering and washing containing ethanol, water again, obtains 23.5g solid product.Add 280g dimethyl sulfoxide (DMSO) stirring and dissolving at 70 ℃, with a small amount of insoluble matter of 60 eye mesh screen filtering, obtain clear solution, be perfluor sulfonyl dicyanamide lighium polymer electrolyte solution.Through distillation and concentration to concentration, be about 10% again, obtain perfluor sulfonyl dicyanamide lighium polymer electrolyte concentrate stand-by.After insoluble matter washing is dry, weigh heavily about 1g, polymer yield 90% (pressing sulfuryl fluoride resin raw material Mass Calculation).
(4) by coating machine coating for the polymer dielectric concentrate making in step (3), blade coating device blade coating film forming, after just doing, add extractant ethanol/water (1:2) mixed liquid dipping, displacement dimethyl sulfoxide (DMSO) two-step film forming, demoulding final vacuum is dry, 140 ℃ of heat treatment 0.5h, after cooling, obtain perfluor sulfonyl dicyanamide lithium (single lithium ion) polymer dielectric film as shown in Figure 1, its fluorine nuclear magnetic spectrum as shown in Figure 2.
The preparation method of above-mentioned the present embodiment mainly adopts the similar transformation method of polymer, makes to take the dielectric film that carbon-chain structure that perfluor replaces contains sulphonyl dicyanamide lithium group as main chain, ethyoxyl side chain terminal; This system is by the crystalline texture of main chain densification, and in the charge effect of side chain and bulk effect inhibition electrolyte, the migration of anion and organic solvent molecule sees through, thereby obtains single cation transport.
The lithium-sulfur rechargeable battery of the present embodiment, comprises cathode of lithium, anode pole piece, dielectric film, organic electrolyte; Dielectric film is the perfluor sulfonyl dicyanamide lighium polymer dielectric film that above-mentioned the present embodiment preparation method obtains;
Cathode of lithium mainly comprises lithium metal;
Anode pole piece is mainly comprised of the collector (being preferably aluminium foil or aluminium net) of conduction current and the positive electrode active materials, conductive agent and the adhesive that are coated on collector; Positive electrode active materials is carbon sulphur polymer; Conductive agent is carbon-based conductive agent, as preferred conductive carbon black, acetylene black or graphite powder; Adhesive is Kynoar; Wherein, the mass percent of positive electrode active materials, conductive agent and adhesive is respectively 70%, 19% and 11%; By ball milling mixing 3h～4h such as positive electrode active materials, conductive agent and adhesives, use coating machine to prepare the anode pole piece of double-coated, positive electrode active materials carrying capacity is 6mg/cm
2, tailor as the anode pole piece that 10cm is long, 5cm is wide 60 ℃ of vacuumize 12h;
By anode pole piece and perfluor sulfonyl dicyanamide lighium polymer dielectric film, lithium paper tinsel, in glove box curls inward around being prepared into battery core, lithium paper tinsel thickness used is 100 μ m, then adds lithium hexafluoro phosphate/DME/DOL electrolyte of 1M, places 24h after encapsulation, tests its electrical property.
Li-S secondary cell prepared by the present embodiment carries out the test of C/10 charge-discharge performance, and under room temperature, limiting voltage is 2.5V～1.5V, and electric current is 0.75mA/cm
2.In the 5th cyclic discharge capacity, 110 energy capacities of charge and discharge cycles keep 81.4% (referring to Fig. 3).
Embodiment 2:
A perfluor sulfonyl dicyanamide lighium polymer electrolyte preparation method of the present invention, comprises the following steps:
(1) 1.5g the third two eyeballs are dissolved in the mixed solvent of 25g methyl phenyl ethers anisole and 5gN-methyl pyrrolidone, then splash in the 250ml single port flask that 0.71g lithium hydride is housed, under nitrogen atmosphere, 30 ℃ of return stirrings reaction 6 hours, make the mixed solution containing malononitrile lithium, remove by filter unreacted raw material lithium hydride and precipitation accessory substance etc., obtain the malononitrile lithium solution of light red clear.
(2) in the above-mentioned malononitrile lithium solution after purifying, add 25g with the perfluor sulfonyl fluororesin of ethyoxyl side chain, the ion exchange capacity of perfluor sulfonyl fluororesin used is 1.0mmol/100g, under nitrogen atmosphere, 70 ℃ of stirring and refluxing reaction 15 hours, obtain side chain containing the electrolytical solution of perfluor sulfonyl dicyanamide lighium polymer of dicyanamide lithium group.
(3) solution system obtaining after similar transformation reaction in step (2) is carried out to suction filtration and obtain solid polymer crude product, solid polymer is dry after the mixed solvent filtering and washing containing ethanol, water again, obtains 23.65g solid product.Add 280g dimethyl sulfoxide (DMSO) stirring and dissolving at 70 ℃, with a small amount of insoluble matter of 60 eye mesh screen filtering, obtain clear solution, be perfluor sulfonyl dicyanamide lighium polymer electrolyte solution.Through distillation and concentration to concentration, be about 10% again, obtain perfluor sulfonyl dicyanamide lighium polymer electrolyte concentrate stand-by.After insoluble matter washing is dry, weigh heavily about 0.8g, polymer yield 91.2% (pressing sulfuryl fluoride resin raw material Mass Calculation).
(4) by coating machine coating for the polymer dielectric concentrate making in step (3), blade coating device blade coating film forming, after just doing, add extractant ethanol/water (1:2) mixed liquid dipping, displacement dimethyl sulfoxide (DMSO) two-step film forming, demoulding final vacuum is dry, 140 ℃ of heat treatment 0.5h, obtain perfluor sulfonyl dicyanamide lighium polymer dielectric film after cooling.
The preparation method of above-mentioned the present embodiment mainly adopts the similar transformation method of polymer, makes to take the dielectric film that carbon-chain structure that perfluor replaces contains sulphonyl dicyanamide lithium group as main chain, ethyoxyl side chain terminal; This system is by the crystalline texture of main chain densification, and in the charge effect of side chain and bulk effect inhibition electrolyte, the migration of anion and organic solvent molecule sees through, thereby obtains single cation transport.
The lithium-sulfur rechargeable battery of the present embodiment, comprises cathode of lithium, anode pole piece, dielectric film, organic electrolyte; Dielectric film is the perfluor sulfonyl dicyanamide lighium polymer dielectric film that above-mentioned the present embodiment preparation method obtains;
Cathode of lithium mainly comprises lithium metal;
Anode pole piece is mainly comprised of the collector (being preferably aluminium foil or aluminium net) of conduction current and the positive electrode active materials, conductive agent and the adhesive that are coated on collector; Positive electrode active materials is carbon sulphur polymer; Conductive agent is carbon-based conductive agent, as preferred conductive carbon black, acetylene black or graphite powder; Adhesive is Kynoar; Wherein, the mass percent of positive electrode active materials, conductive agent and adhesive is respectively 70%, 19% and 11%; By ball milling mixing 3h～4h such as positive electrode active materials, conductive agent and adhesives, use coating machine to prepare the anode pole piece of double-coated, positive electrode active materials carrying capacity is 6mg/cm
2, tailor as the anode pole piece that 10cm is long, 5cm is wide 60 ℃ of vacuumize 12h;
By anode pole piece and perfluor sulfonyl dicyanamide lighium polymer dielectric film, lithium paper tinsel, in glove box curls inward around being prepared into battery core, lithium paper tinsel thickness used is 100 μ m, then adds lithium hexafluoro phosphate/DME/DOL electrolyte of 1M, places 24h after encapsulation, tests its electrical property.
Li-S secondary cell prepared by the present embodiment carries out the test of C/10 charge-discharge performance, and under room temperature, limiting voltage is 2.5V～1.5V, and electric current is 0.75mA/cm
2.In the 5th cyclic discharge capacity, 101 energy capacities of charge and discharge cycles keep 81.4% (referring to Fig. 4).
Claims (10)
1. a perfluor sulfonyl dicyanamide lighium polymer electrolyte preparation method with higher yields, comprises the following steps:
(1) by malononitrile and lithium hydride under specific blend solvent orange 2 A exists under proper temperature and inert atmosphere hybrid reaction, the reaction time is no less than 5h, prepares malononitrile lithium solution;
(2) be there is to similar transformation reaction to the perfluor sulfonyl fluororesin with ethyoxyl side chain in the above-mentioned malononitrile lithium solution after purifying, it is excessive that malononitrile lithium keeps, reacted by subsequent treatment, obtained side chain containing the perfluor sulfonyl dicyanamide lighium polymer electrolyte of dicyanamide lithium group.
2. preparation method according to claim 1, is characterized in that: in described step (1), lithium hydride reacts with the mol ratio equivalent of malononitrile with 2:1, and control lithium hydride should be excessive, and excessive ratio is 1%～80%.
3. preparation method according to claim 1, is characterized in that: in described step (1), the actual conditions of hybrid reaction for to react 5h～40h under 20 ℃～100 ℃ return stirring conditions.
4. preparation method according to claim 1, it is characterized in that: in described step (1), described specific blend solvent orange 2 A is the mixed system of methyl phenyl ethers anisole and 1-METHYLPYRROLIDONE, and the mass ratio of methyl phenyl ethers anisole and 1-METHYLPYRROLIDONE is 20: 1～2: 1, the addition of described specific blend solvent orange 2 A is 10～50 times of malononitrile quality.
5. according to the preparation method described in any one in claim 1～4, it is characterized in that: in described step (2), the actual conditions of similar transformation reaction is stirring and refluxing reaction 4h～30h under the inert atmosphere of 40 ℃～120 ℃.
6. preparation method according to claim 5, it is characterized in that: in described step (2), subsequent treatment refers to that the polymer precipitation that described similar transformation reaction is generated is after filtering and washing, add solvent B stirring and dissolving at 30 ℃～100 ℃, then a small amount of insoluble matter of filtering obtains perfluor sulfonyl dicyanamide lighium polymer electrolyte solution; Through distillation and concentration, obtain perfluor sulfonyl dicyanamide lighium polymer electrolyte concentrate again.
7. preparation method according to claim 6, it is characterized in that: described subsequent treatment also comprises: by coating machine coating for the polymer dielectric concentrate making, blade coating device blade coating film forming or casting film-forming, after just doing, add extractant two-step film forming, after vacuumize, 120 ℃～200 ℃ heat treatment 0.5h～4h, obtain perfluor sulfonyl dicyanamide lighium polymer dielectric film after cooling; Selected extractant is at least one in ethanol, isopropyl alcohol, ether, propyl ether, oxolane, ethylene carbonate, propene carbonate, diethyl carbonate, methyl ethyl carbonate, dioxolane, water, carrene, dichloroethanes, toluene, dimethylbenzene.
8. preparation method according to claim 6, is characterized in that: described solvent B is one or both the mixing in methyl phenyl ethers anisole, 1-METHYLPYRROLIDONE, N-ethyl pyrrolidone, dichloroethanes, dimethyl sulfoxide (DMSO), sulfolane, water, triglyme, tetraethylene glycol dimethyl ether.
9. preparation method according to claim 8, it is characterized in that: described specific blend solvent orange 2 A is identical with the part composition of solvent B, and specific blend solvent orange 2 A and solvent B are the mixed solvent system that comprises methyl phenyl ethers anisole, make solids content wherein reach 4%～50% after adding solvent B.
10. a lithium-sulfur rechargeable battery, comprises cathode of lithium, anode pole piece, dielectric film, organic electrolyte; It is characterized in that:
The electrolyte that described dielectric film is used is the perfluor sulfonyl dicyanamide lighium polymer electrolyte that in claim 1～9, described in any one, preparation method obtains;
Described cathode of lithium mainly comprises the negative active core-shell material that lithium metal or lithium alloys form;
Described anode pole piece is mainly comprised of the collector of conduction current and positive electrode active materials, conductive agent and the adhesive being coated on collector; Described positive electrode active materials is at least one in sulphur simple substance, organic sulfur compound, carbon sulphur polymer;
Described organic electrolyte comprises lithium salts and nonaqueous solvents, and described lithium salts is selected from least one in the poly-sulphur lithium of lithium hexafluoro phosphate, LiBF4, hexafluoroarsenate lithium, lithium perchlorate, lithium trifluoromethanesulp,onylimide, trifluoromethyl sulfonic acid lithium, lithium nitrate, different valence state, described nonaqueous solvents comprises acetonitrile, cyclohexane, cyclohexanone, isopropyl alcohol, oxolane, 2-methyltetrahydrofuran, ethylene carbonate, propene carbonate, butylene, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, methyl formate, Ethyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, dimethoxy-ethane, 1, 3-dioxolane, diethylene glycol dimethyl ether, triglyme, tetraethylene glycol dimethyl ether, glycol dimethyl ether, sulfolane, two methylene sulfones, at least one in dimethyl sulfone.
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| CN1292005A (en) * | 1998-03-03 | 2001-04-18 | 纳幕尔杜邦公司 | Substantially fluorinated ionomers |
| CN1411474A (en) * | 1999-12-21 | 2003-04-16 | 纳幕尔杜邦公司 | Chain transfer agents influoroolefin polymerization |
| CN102983361A (en) * | 2012-11-23 | 2013-03-20 | 中国人民解放军国防科学技术大学 | Electrolyte for Li-S battery, preparation method thereof, and Li-S battery containing same |
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| CN1292005A (en) * | 1998-03-03 | 2001-04-18 | 纳幕尔杜邦公司 | Substantially fluorinated ionomers |
| CN1411474A (en) * | 1999-12-21 | 2003-04-16 | 纳幕尔杜邦公司 | Chain transfer agents influoroolefin polymerization |
| CN102983361A (en) * | 2012-11-23 | 2013-03-20 | 中国人民解放军国防科学技术大学 | Electrolyte for Li-S battery, preparation method thereof, and Li-S battery containing same |
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| ZHAOQING JIN ET AL: "Electrochemical performance of lithium/sulfur batteries using perfluorinated ionomer electrolyte with lithium sulfonyl dicyanomethide functional groups as functional separator", 《RSC ADVANCES》, vol. 3, no. 23, 28 March 2013 (2013-03-28), pages 8889 - 8898 * |
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