CN105261742A - Chalcogenide semi-solid lithium battery and preparing method thereof - Google Patents

Chalcogenide semi-solid lithium battery and preparing method thereof Download PDF

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CN105261742A
CN105261742A CN201510843891.1A CN201510843891A CN105261742A CN 105261742 A CN105261742 A CN 105261742A CN 201510843891 A CN201510843891 A CN 201510843891A CN 105261742 A CN105261742 A CN 105261742A
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semisolid
lithium
sulphur
polymer
lithium battery
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CN105261742B (en
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田文生
汤卫平
吴勇民
徐碇皓
施斌
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Shanghai Institute of Space Power Sources
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Abstract

The invention discloses a chalcogenide semi-solid lithium battery and a preparing method thereof. The battery is formed by stacking a semi-solid chalcogenide positive electrode, a semi-solid electrolyte and a lithium wafer negative electrode. The semi-solid chalcogenide positive electrode is prepared through the process that firstly, a lithium-salt-containing polymer, a chalcogenide material and a carbon conductive agent are mixed into semi-solid, and then aluminum foil or a nickel net serves as a current collector. The semi-solid electrolyte is prepared by mixing porous inorganic oxide and a lithium-salt-containing polymer, wherein the lithium-salt-containing polymer is prepared by mixing a flow-state polymer and lithium salt. According to the composite type semi-solid electrolyte and the semi-solid chalcogenide positive electrode formed by compounding the lithium-salt-containing polymer and the chalcogenide material, the advantages that inorganic materials are high in mechanical strength and good in stability and the polymer materials are good in flexibility and interface contact, high in ionic conductivity and the like are combined, the ionic conductivity of the electrolyte and the energy storage stability of the chalcogenide positive electrode are improved, the first-time specific discharge capacity is 375 mAh/g, a discharging platform exceeds 2V, an energy storage mechanism is novel, and an energy storage power source with large potential is obtained.

Description

A kind of sulphur system semisolid lithium battery and preparation method thereof
Technical field
The invention belongs to novel solid lithium battery technical field in energy-storage battery field, relate to a kind of lithium battery, specifically, relate to the preparation method of a kind of sulphur system semisolid lithium battery.
Background technology
In the lithium battery technology of future generation and product of alternative lithium ion battery, solid lithium battery receives much concern.The lithium secondary battery that solid lithium battery is collector, both positive and negative polarity, electrolyte all adopt solid-state material.Compare with existing lithium ion battery, completely not containing electrolyte in solid lithium battery system, not containing binding agent, conductive agent in positive/negative plate, structure is simply fine and close, and energy density Improvement is huge; Not containing any liquid parts in solid electrolyte, therefore solid lithium battery completely need not concern about disclosure problem, ensure that high security; Solid electrolyte has higher machinery and thermal stability, can not undergo phase transition, and while ensure that cycle life, makes its easier and integrated formation integrated instrument of device.In sum, the performance characteristics of solid lithium battery can meet the application demand of developing spacecraft and Military Power well, and development solid lithium battery meets the developing direction of the great basic research of China.
CymbetCorporation, InfinitePowerSolutions, SAKTI3, SEEObatteries, the solid lithium battery production marketing of company's prior art comparative maturities such as TeledyneElectronicTechnologies, can as the micro battery of the aspects such as smart card, transducer, microelectronics and micro mechanical system.These film lithium cell cycle lives are greater than tens thousand of times, and useful life is many more than 10 years, and can tolerate higher temperature, thickness is many at below 1mm.But solid electrolyte ionic conductance is low, be difficult to do thick; Simultaneously, inorganic solid electrolyte pliability is low, can not tolerate shock and extruding that lithium ion battery can bear, very easily cracked and can not superpose after enlarged leather area, cause the solid lithium battery majority rank when microampere can commercially produced at present, application is restricted.Consider that polymer flexibility is large, the advantage such as Stability Analysis of Structures in easy film forming and inorganic solid electrolyte course of reaction, the present invention, by introducing the functional unit of this flexibility of polymer, alleviates all kinds of stress that battery is subject to, thus realize the preparation of Large Copacity solid lithium battery, improve its practical value.
Summary of the invention
The object of the invention is the problem low for solid lithium battery system intermediate ion conductivity, capacity is not high, utilize the feature that mobility polymer ions conductivity is high and sulfide capacity is high, the sulphur system semisolid lithium battery of Development of Novel, improves solid lithium battery inner ion conductivity and battery capacity.
For achieving the above object, the invention provides a kind of sulphur system semisolid lithium battery, this battery is by semisolid sulphur system positive pole, semisolid electrolyte and lithium sheet negative pole is stacking is formed; Described semisolid sulphur system positive pole is first mixed into semisolid by containing lithium salts polymer, sulphur based material, carbonaceous conductive agent, then with aluminium foil or nickel screen for collector is formed; Described semisolid electrolyte is formed with containing lithium salts polymer mixed by porous inorganic oxide; Described is mixed by flowable state polymer and lithium salts containing lithium salts polymer.
Carrying sulfur content in described semisolid sulphur system positive pole is 45% ~ 65%, is calculated in mass percent.
Described sulphur based material selects elemental sulfur, organic sulfur compound (as polyacrylonitrile sulphur) and sulphur carbon composite (as sulphur mesoporous carbon composite material, sulfur graphite alkene composite material) etc.
Any one or two or more mixtures in superP, VGCF, CNT, organic polymer conductive agent are selected in described carbonaceous conductive agent.
Described porous inorganic oxide is the micro-nano porous material containing more than 0.5nm aperture, selects na-pretreated zeolite or ferrierite (FER) or the mixing of the two.Described na-pretreated zeolite selects AlNaO 6si 2.
Described flowable state polymer is for being dissolved with the PEG macromolecule that mass fraction is 6 ~ 12wt% lithium salts, and its degree of polymerization is not more than 1000, and the lithium salts of dissolving is LiCF 3sO 3, LiClO 4, LiPF 6, LiBF 4in one or more mixture.
Present invention also offers a kind of preparation method of above-mentioned sulphur system semisolid lithium battery, the method comprises:
Step 1, the preparation containing lithium salts polymer: lithium salts is distributed in flowable state polymer, is stirred to and dissolves completely, obtain containing lithium salts be calculated in mass percent be 6 ~ 12wt% containing lithium salts polymer solution;
Step 2, the electrolytical preparation of semisolid: that step 1 is prepared mixes with porous inorganic oxide containing lithium salts polymer, until solution is all adsorbed onto in the hole of porous inorganic oxide, does not have liquid mobile phase, make film again, obtain semisolid electrolytic thin-membrane;
Step 3, the preparation of semisolid sulphur positive pole: by sulphur based material, be fully mixed into paste containing lithium salts polymer and carbonaceous conductive agent, then make film, make collector with aluminium foil or nickel screen, obtains semisolid sulphur positive pole;
Step 4, the preparation of semisolid lithium battery: adopt stacking mode to insert battery case assembling at semisolid sulphur system positive pole, semisolid electrolyte, lithium sheet negative pole successively and make semisolid lithium battery.
The present invention utilizes ball-milling method sulphur based material and conductive agent to be distributed in semisolid lithium-ion electrolyte (namely containing lithium salts polymer), obtains paste semisolid sulphur system positive electrode.This paste positive electrode is placed in collector rolls and is pressed into thin slice, form the semi-solid bonding anode material of lithium battery simultaneously with high power capacity, high conductivity, high ionic conductivity.
Described porous inorganic oxide need carry out preliminary treatment, this preliminary treatment refers to that this porous inorganic oxide is in the ball grinder of 200 ~ 400r/min after ball milling 2 ~ 8h at rotating speed, at room temperature ion-exchange is carried out, afterwards 400 ~ 450 DEG C of heat treatment 3 ~ 6h in Muffle furnace with lithium salts.
Described ion-exchange lithium salts is the aqueous solution that concentration is not less than 3M, and solute selects LiNO 3, LiCl, LiClO 4in any one or two or more mixtures.
The present invention with porous inorganic oxide stable in air for skeleton, fill in duct and there is the strong polymer of certain fluidity, ionic conduction ability or polymer precursor is ion conducting medium, utilize loose structure high-ratio surface sum micro-nano hole footpath size to the constraint effect of fluidity substance, preparation is not containing the solid-state and semi-solid bonding type solid electrolyte of liquid.
Beneficial effect of the present invention is as follows:
Sulphur system semisolid lithium battery prepared by the present invention, owing to have employed sulphur system positive electrode, has higher specific capacity; Sulphur is scattered in in the organic/inorganic composite material of high ionic conductivity in conductive agent material with carbon element, and its surface electronic and ion conduction rate are obtained for lifting, thus can give play to higher gram volume; The mobility polymer be bound by porous inorganic oxide improves contact area and the wettability of electrolyte and electrode, significantly reduces interface resistance, shows good ionic conductivity; Porous inorganic oxide is not only composite electrolyte and provides higher mechanical strength and larger specific area, self stability is strong simultaneously, also for composite electrolyte provides certain ionic conductivity, improve practicality that is solid-state and semi-solid bonding type solid electrolyte.
Accompanying drawing explanation
Fig. 1 is semisolid lithium battery structure figure of the present invention.
Fig. 2 is example 1 semisolid dielectric film of the present invention.
Fig. 3 is example 3 sulphur system of the present invention semisolid lithium battery discharge curve.
specific embodiment party
As shown in Figure 1, be the internal structure of a kind of sulphur system provided by the invention semisolid lithium battery, this battery main body is formed with lithium sheet negative pole 3 is stacking by semisolid sulphur system positive pole 1, semisolid electrolyte 2; Described semisolid sulphur system positive pole 1 is first mixed into semisolid by containing lithium salts polymer, sulphur based material, carbonaceous conductive agent, then with aluminium foil or nickel screen for collector is formed; Described semisolid electrolyte 2 is formed with containing lithium salts polymer mixed by porous inorganic oxide; Described is mixed by flowable state polymer and lithium salts containing lithium salts polymer.This lithium battery take porous inorganic oxide as skeleton, flowable state polymer is ion-conducting material, lithium salts compensates for ion transfer, utilize loose structure high-ratio surface sum micro-nano hole footpath size to the constraint effect of fluidity substance, preparation not containing the solid-state and semi-solid bonding type solid electrolyte of liquid, and defines the semi-solid bonding anode material of lithium battery simultaneously with high power capacity, high conductivity, high ionic conductivity.
The preparation method of lithium battery of the present invention is as follows:
(1) the electrolytical preparation of semisolid
With porous inorganic oxide stable in air for skeleton, fill in duct and there is the strong polymer of certain fluidity, ionic conduction ability or polymer precursor is ion conducting medium, utilize loose structure high-ratio surface sum micro-nano hole footpath size to the constraint effect of fluidity substance, preparation is not containing the solid-state and semi-solid bonding type solid electrolyte of liquid.
Described porous inorganic oxide adopts na-pretreated zeolite, ferrierite (FER) etc., and carry out a series of ball milling, with the preliminary treatment such as the ion-exchange of lithium salts room temperature, heat treatment.This preliminary treatment specifically refers to, porous inorganic oxide rotational speed of ball-mill is 200 ~ 400r/min, and the time is 2 ~ 8h, to reduce porous inorganic oxide particle size; Ion-exchange lithium salts is LiNO 3, LiCl, LiClO 4deng the aqueous solution, the object of ion-exchange is lithium ion by sodium ion in porous inorganic oxide etc. by ion-exchange; 400 ~ 450 DEG C of heat treatment 3 ~ 6h in Muffle furnace, object is the crystallization water in removing porous inorganic oxide.
Described mobility polymer selects PEG200, PEG400, PEG600 etc., and LiCF selected by lithium salts 3sO 3, LiClO 4, LiPF 6, LiBF 4deng.By a certain percentage lithium salts is dissolved in mobility polymer solvent, magnetic agitation certain hour obtain certain viscosity containing lithium salts polymer solution.
By porous inorganic oxide after above-mentioned preliminary treatment and containing lithium salts polymer solution hand-ground certain hour in mortar by a certain percentage, be all adsorbed onto in porous inorganic oxide hole to solution, there is no liquid mobile phase.Finally this blend sample is rolled and be pressed into certain thickness semitransparent thin film, obtain semisolid electrolyte.
(2) the sulphur system positive pole preparation of semisolid electrolyte compound
Take sulfur-bearing positive electrode (i.e. sulphur based material), conductive agent by a certain percentage and contain lithium salts polymer, the sulphur system positive electrode mixed is obtained with the method such as hand-ground or ball milling, certain thickness film is made by rolling the methods such as pressure, coating, with aluminium foil, nickel screen etc. for collector, obtain sulphur system positive pole.Described sulfur-bearing positive electrode is elemental sulfur, organic sulfur compound (as polyacrylonitrile sulphur), sulphur material with carbon element (as sulphur mesoporous carbon composite material, sulfur graphite alkene composite material) etc.
(3) sulphur system semisolid lithium battery preparation
Adopt stacking mode to insert button cell stainless steel case with lithium sheet negative pole 3 in semisolid sulphur system positive pole 1, semisolid electrolyte 2 successively, wherein, copper is negative collector, is assembled into button cell and tests in glove box.
Below in conjunction with embodiment and accompanying drawing, the specific embodiment of the present invention is further described.
Embodiment 1:
(1) zeolite preliminary treatment: by 10g na-pretreated zeolite powder (AlNaO 6si 2, molecular weight 202.10) and be dispersed in the lithium nitrate (LiNO that 150-250ml concentration is 3M 3) in the aqueous solution, room temperature lower magnetic force stirs decompress filter after 12 ~ 24h, and spend deionized water three times, after oven dry, in Muffle furnace, 400 ~ 450 DEG C of heat treatment 4h are for subsequent use.With the rotating speed high energy dry type ball milling 2 ~ 8h of 400r/min, zeolite powder after white floury preliminary treatment will be obtained by zeolite after process.
(2) prepare containing lithium salts polymer: the trifluoromethyl sulfonic acid lithium (LiCF taking certain mass 3sO 3), be distributed in PEG400 (PEG400) solvent, magnetic agitation 12 ~ 24h, to trifluoromethyl sulfonic acid lithium (LiCF 3sO 3) dissolve completely, obtain the trifluoromethyl sulfonic acid lithium (LiCF of viscosity about 180 ~ 200mPaS 3sO 3) mass fraction is PEG400 (PEG400) solution of 6 ~ 12wt%.
(3) semisolid electrolyte preparation: after preliminary treatment zeolite with containing 6 ~ 12wt% trifluoromethyl sulfonic acid lithium (LiCF 3sO 3) PEG400 (PEG400) solution hand-ground 20 ~ 40min in mortar by a certain percentage, be all adsorbed onto in zeolite pores to solution, there is no liquid mobile phase, in grains of sand shape or paste.Finally this blend sample is rolled and be pressed into the semitransparent thin film (as shown in Figure 2) that thickness is 200 ~ 500 μm, obtain semisolid electrolytic thin-membrane.
(4) semisolid sulphur system positive pole preparation: 5:3:1 takes sublimed sulfur (S), containing 6wt% ~ 12wt% trifluoromethyl sulfonic acid lithium (LiCF in mass ratio 3sO 3) PEG400 (PEG400) solution, conductive agent (superP), put into agate jar, high-energy ball milling 2 ~ 10h under the rotating speed of 300 ~ 450r/min, obtain black paste semisolid sulphur system positive electrode.This paste positive electrode is rolled and is pressed into the film that thickness is 100 ~ 500 μm, with aluminium foil, nickel screen etc. for collector, obtain the semisolid sulphur system positive pole carrying sulfur content 56%.
(5) semisolid lithium battery preparation: adopt stacking mode (as Fig. 1) to insert 2016 type button cell shells at semisolid sulphur system positive pole, semisolid electrolyte, lithium sheet negative pole successively, be assembled into button cell and test in glove box.
Embodiment 2:
(1) zeolite preliminary treatment: 10g ferrierite powder (FER) is dispersed in the lithium perchlorate (LiClO that 150-250ml concentration is 3M 4) in the aqueous solution, room temperature lower magnetic force stirs decompress filter after 24 ~ 36h, and spend deionized water three times, after oven dry, in Muffle furnace, 400 ~ 450 DEG C of heat treatment 4h are for subsequent use.With the rotating speed high energy dry type ball milling 2 ~ 8h of 400r/min, zeolite powder after white floury preliminary treatment will be obtained by zeolite after process.
(2) prepare containing lithium salts polymer: the lithium perchlorate (LiClO taking certain mass 4), be distributed in PEG400 (PEG400) solvent, magnetic agitation 12 ~ 24h, to lithium perchlorate (LiClO 4) dissolve completely, obtain the lithium perchlorate (LiClO of viscosity about 160 ~ 200mPaS 4) mass fraction is PEG400 (PEG400) solution of 10 ~ 16wt%.
(3) semisolid electrolyte preparation: after preliminary treatment zeolite with containing 10 ~ 16wt% lithium perchlorate (LiClO 4) PEG400 (PEG400) solution hand-ground 20 ~ 40min in mortar by a certain percentage, be all adsorbed onto in zeolite pores to solution, there is no liquid mobile phase, in grains of sand shape or paste.Finally this blend sample is rolled and be pressed into the semitransparent thin film that thickness is 200 ~ 500 μm, obtain semisolid electrolytic thin-membrane.
(4) semisolid sulphur system positive pole preparation: 5:3:1 takes sublimed sulfur (S), containing 10wt% ~ 16wt% lithium perchlorate (LiClO in mass ratio 4) PEG400 (PEG400) solution, conductive agent (superP), put into agate jar, high-energy ball milling 2 ~ 10h under the rotating speed of 300 ~ 450r/min, obtain black paste semisolid sulphur system positive electrode.This paste positive electrode is rolled and is pressed into the film that thickness is 100 ~ 500 μm, with aluminium foil, nickel screen etc. for collector, obtain the semisolid sulphur system positive pole carrying sulfur content 56%.
(5) semisolid lithium battery preparation: adopt stacking mode (as Fig. 1) to insert 2016 type button cell shells at semisolid sulphur system positive pole, semisolid electrolyte, lithium sheet negative pole successively, be assembled into button cell and test in glove box.
Embodiment 3:
(1) zeolite preliminary treatment: by 10g na-pretreated zeolite powder (AlNaO 6si 2, molecular weight 202.10) and be dispersed in the lithium nitrate (LiNO that 150-250ml concentration is 3M 3) in the aqueous solution, room temperature lower magnetic force stirs decompress filter after 12 ~ 24h, and spend deionized water three times, after oven dry, in Muffle furnace, 400 ~ 450 DEG C of heat treatment 4h are for subsequent use.By zeolite after process with the rotating speed high energy dry type ball milling 2 ~ 8h of 400r/min, zeolite powder after the preliminary treatment of acquisition floury.
(2) prepare containing lithium salts polymer: the trifluoromethyl sulfonic acid lithium (LiCF taking certain mass 3sO 3), be distributed in PEG400 (PEG400) solvent, magnetic agitation 12 ~ 24h, to trifluoromethyl sulfonic acid lithium (LiCF 3sO 3) dissolve completely, obtain the trifluoromethyl sulfonic acid lithium (LiCF of viscosity about 180 ~ 200mPaS 3sO 3) mass fraction is PEG400 (PEG400) solution of 6 ~ 12wt%.
(3) semisolid electrolyte preparation: after preliminary treatment zeolite with containing 6 ~ 12wt% trifluoromethyl sulfonic acid lithium (LiCF 3sO 3) PEG400 (PEG400) solution hand-ground 20 ~ 40min in mortar by a certain percentage, be all adsorbed onto in zeolite pores to solution, there is no liquid mobile phase, in grains of sand shape or paste.Finally this blend sample is rolled and be pressed into the semitransparent thin film (as Fig. 2) that thickness is 200 ~ 500 μm, obtain semisolid electrolytic thin-membrane.
(4) semisolid sulphur system positive pole preparation: 6:3:1 takes polyacrylonitrile-sulphur (PAN-S), containing 6wt% ~ 12wt% trifluoromethyl sulfonic acid lithium (LiCF in mass ratio 3sO 3) PEG400 (PEG400) solution, conductive agent (superP), put into agate jar, high-energy ball milling 2 ~ 10h under the rotating speed of 300 ~ 450r/min, obtain black paste semisolid sulphur system positive electrode.This paste positive electrode is rolled and is pressed into the film that thickness is 100 ~ 500 μm, with aluminium foil, nickel screen etc. for collector, obtain the semisolid sulphur system positive pole carrying sulfur content 40%.
(5) semisolid lithium battery preparation: adopt stacking mode (as Fig. 1) to insert 2016 type button cell shells at semisolid sulphur system positive pole, semisolid electrolyte, lithium sheet negative pole successively, be assembled into button cell and test in glove box.Discharge curve is as shown in Figure 3 first for battery, battery is with the current density of 10mA/g sulphur, charge and discharge cycles is carried out at 2.8 ~ 1.5V voltage range under room temperature, first discharge specific capacity is 375mAh/g, discharge platform more than 2V higher than traditional lithium-sulfur cell, illustrating that it has novel energy storage mechanism, is the accumulation power supply that a kind of practical potentiality are larger.
In sum, the present invention with porous inorganic oxide stable in air for skeleton, fill in duct and there is the strong polymer of certain fluidity, ionic conduction ability or polymer precursor is ion conducting medium, improve pliability and the ionic conductivity of electrolytic thin-membrane, utilize loose structure high-ratio surface sum micro-nano hole footpath size to the constraint effect of fluidity substance, prepare not containing the hybrid solid-state electrolyte of liquid; By the sulphur based material compound of this compound semisolid electrolyte and high power capacity, form ionic conductivity high, the positive pole that specific capacity is also high simultaneously; Be negative pole with lithium metal, prepare novel sulphur system semisolid lithium battery.
The compound semisolid electrolyte that the present invention proposes first and the semisolid sulphur system positive pole containing lithium salts polymer and sulphur based material compound, by high for inorganic material mechanical strength, good stability and polymeric material pliability is good, interracial contact is good, ionic conductivity advantages of higher combines, improve the ionic conductivity of composite electrolyte and the energy storage stability of sulphur system positive pole, first discharge specific capacity is 375mAh/g, discharge platform is more than 2V, higher than traditional lithium-sulfur cell, illustrating that it has novel energy storage mechanism, is the accumulation power supply that a kind of practical potentiality are larger.
Although content of the present invention has done detailed introduction by above preferred embodiment, will be appreciated that above-mentioned description should not be considered to limitation of the present invention.After those skilled in the art have read foregoing, for multiple amendment of the present invention and substitute will be all apparent.Therefore, protection scope of the present invention should be limited to the appended claims.

Claims (10)

1. a sulphur system semisolid lithium battery, is characterized in that, this battery is by semisolid sulphur system positive pole (1), semisolid electrolyte (2) and lithium sheet negative pole (3) is stacking is formed; Described semisolid sulphur system positive pole (1) is first mixed into semisolid by containing lithium salts polymer, sulphur based material, carbonaceous conductive agent, then with aluminium foil or nickel screen for collector is formed; Described semisolid electrolyte (2) is formed with containing lithium salts polymer mixed by porous inorganic oxide; Described is mixed by flowable state polymer and lithium salts containing lithium salts polymer.
2. sulphur system as claimed in claim 1 semisolid lithium battery, is characterized in that, carrying sulfur content in described semisolid sulphur system positive pole is 45% ~ 65%, is calculated in mass percent.
3. sulphur system as claimed in claim 1 semisolid lithium battery, is characterized in that, described sulphur based material select in elemental sulfur, organic sulfur compound or sulphur carbon composite any one.
4. sulphur system as claimed in claim 1 semisolid lithium battery, is characterized in that, any one or two or more mixtures in superP, VGCF, CNT, organic polymer conductive agent are selected in described carbonaceous conductive agent.
5. sulphur system as claimed in claim 1 semisolid lithium battery, it is characterized in that, described porous inorganic oxide is the micro-nano porous material containing more than 0.5nm aperture, selection na-pretreated zeolite or ferrierite or the mixing of the two.
6. sulphur system as claimed in claim 5 semisolid lithium battery, is characterized in that, described na-pretreated zeolite selects AlNaO 6si 2.
7. sulphur system as claimed in claim 1 semisolid lithium battery, it is characterized in that, described flowable state polymer is for being dissolved with the PEG macromolecule that mass fraction is 6 ~ 12wt% lithium salts, and its degree of polymerization is not more than 1000, and the lithium salts of dissolving is LiCF 3sO 3, LiClO 4, LiPF 6, LiBF 4in one or more mixture.
8., as a preparation method for the sulphur system semisolid lithium battery in claim 1-7 as described in any one, it is characterized in that, the method comprises:
Step 1, the preparation containing lithium salts polymer: lithium salts is distributed in flowable state polymer, is stirred to and dissolves completely, obtain containing lithium salts be calculated in mass percent be 6 ~ 12wt% containing lithium salts polymer solution;
Step 2, the electrolytical preparation of semisolid: that step 1 is prepared mixes with porous inorganic oxide containing lithium salts polymer, until solution is all adsorbed onto in the hole of porous inorganic oxide, then makes film, obtains semisolid electrolytic thin-membrane;
Step 3, the preparation of semisolid sulphur positive pole: by sulphur based material, be fully mixed into paste containing lithium salts polymer and carbonaceous conductive agent, then make film, make collector with aluminium foil or nickel screen, obtains semisolid sulphur positive pole;
Step 4, the preparation of semisolid lithium battery: adopt stacking mode to insert battery case assembling at semisolid sulphur system positive pole, semisolid electrolyte, lithium sheet negative pole successively and make semisolid lithium battery.
9. the preparation method of sulphur system as claimed in claim 8 semisolid lithium battery, it is characterized in that, described porous inorganic oxide need carry out preliminary treatment, this preliminary treatment refers to that this porous inorganic oxide is in the ball grinder of 200 ~ 400r/min after ball milling 2 ~ 8h at rotating speed, at room temperature ion-exchange is carried out, afterwards 400 ~ 450 DEG C of heat treatment 3 ~ 6h in Muffle furnace with lithium salts.
10. the preparation method of sulphur system as claimed in claim 9 semisolid lithium battery, it is characterized in that, described ion-exchange lithium salts is the aqueous solution that concentration is not less than 3M, and solute selects LiNO 3, LiCl, LiClO 4in any one or two or more mixtures.
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