CN106876783B - A kind of all solid state lithium-sulfur cell - Google Patents

Abstract

The invention discloses an all-solid-state lithium-sulfur battery, comprising a sulfur positive electrode, a lithium or lithium alloy negative electrode and a lithiated sulfonic acid polymer solid electrolyte separator; the solid electrolyte separator is located between the sulfur positive electrode and the lithium or lithium alloy negative electrode; the sulfur positive electrode It includes sulfur-containing active material, conductive agent and lithiated sulfonic acid polymer; a sulfur positive electrode, a lithiated sulfonic acid polymer solid electrolyte, and a lithium or lithium alloy negative electrode are stacked and assembled in sequence to form a battery. The room temperature ionic conductivity of the lithiated sulfonic acid polymer solid electrolyte is > ^10-5 S/cm, no complex lithium salt is required, the preparation method is simple, and the room temperature ionic conductivity of the lithiated sulfonic acid polymer solid electrolyte is excellent for general inorganic-organic composite solid electrolytes. The sulfur cathode electrode is prepared by using polymer emulsion, and an efficient "sulfur/carbon/solid electrolyte" interface is constructed inside the electrode, which improves the activity of the sulfur electrode and obtains a battery with excellent performance; and the existing electrode coating process and equipment, which is conducive to large-scale production.

Description

An all-solid-state lithium-sulfur battery

technical field

The invention relates to a lithiated sulfonic acid polymer solid electrolyte, a preparation method thereof, and an all-solid-state lithium-sulfur battery.

Background technique

Lithium-sulfur batteries have become the next generation of new secondary battery systems due to their high energy density and low cost. However, most of the lithium-sulfur batteries reported in the current research use organic electrolytes with lower boiling points, and there are still some technical problems to be solved. 1. The discharge intermediate polysulfide of the sulfur positive electrode is dissolved in the electrolyte, which on the one hand causes the shuttle effect and reduces the Coulomb efficiency; on the other hand, the polysulfide diffuses through the diaphragm to the negative electrode and corrodes the metal lithium. 2. In a battery using an organic electrolyte, due to the uneven deposition of lithium ions, the metal lithium negative electrode is prone to dendrites. On the one hand, the production of dead lithium affects the cycle performance of the battery; on the other hand, the dendrite pierces the separator and causes the battery to short circuit. 3. The organic electrolyte has a low boiling point. In the case of abuse, such as overcharge, overdischarge, and external force acupuncture, the battery will cause dangerous accidents such as burning and explosion.

In view of the above problems, one of the solutions is to replace the organic electrolyte with a solid electrolyte that can conduct lithium ions, that is, to design and prepare an all-solid-state lithium-sulfur battery. So far, the reported solid electrolytes for all-solid-state lithium-sulfur batteries mainly include inorganic solid electrolytes and polymer electrolytes. Inorganic solid electrolytes are further divided into oxide solid electrolytes and sulfide solid electrolytes. The ionic conductivity of oxide inorganic solid electrolytes reported so far is relatively low, while sulfide solid electrolytes have high ionic conductivity (up to 12 mS/cm), but are sensitive to air, making material preparation and battery assembly difficult. In addition, the inorganic solid electrolyte is brittle, difficult to form, and has a large interface impedance with the positive and negative electrodes; the all-solid-state battery prepared by using the inorganic solid electrolyte is not easy to be made into various shapes, and cannot meet the various requirements of modern society for batteries. Polymer electrolytes are divided into dry and gel polymer electrolytes. The room temperature ionic conductivity of dry polymer electrolytes is low (10 ^-9 S/cm), which has not yet been practically applied. Gel polymer electrolytes are usually composed of polymer complex lithium salts, and the room temperature ionic conductivity reaches 10 ^-3 S/cm, which has the possibility of practical application. Most of the gel polymer electrolytes reported so far are composed of polymer complex lithium salts and infiltration solvents, but there are still problems with the dissolution of active substances and the formation of metal lithium dendrites. CN200910043325.7 discloses an all-solid-state lithium-sulfur battery using a polymer solid electrolyte prepared by grafting an organic dihalide main chain with PEO as a matrix and complexing a lithium salt. The ether oxygen groups on the PEO chain can interact with lithium Ion complexation, the function of transporting lithium ions is achieved by the back and forth swing of the polymer main chain; CN201110445406.7 discloses an all-solid-state lithium-sulfur battery using an organic-inorganic composite polymer electrolyte, and the composite electrolyte includes PEO, Li ₄ Ti ₅ O ₁₂ and lithium salt, at 90 degrees, the ionic conductivity of the solid electrolyte is 10 ^-3 S/cm, and the first discharge specific capacity of the sulfur positive electrode is ~ 1500mAh/g; JP2011060649-A discloses a sulfide glass or glass All-solid-state lithium-sulfur battery with ceramic solid electrolyte, the sulfide solid electrolyte is fused to the surface of the electrode material to show high ionic conductivity, and does not react with the electrode active material, preventing the increase of interface resistance; WO2013024537-A1 discloses a lithium Ion conductor Li _3+3/4x B _x P _1-3/4x S ₄ (0.155≤x≤1.3), containing β-Li ₃ PS ₄ , and part of P atoms are replaced by B atoms, reducing the internal resistance of the battery, Improve output characteristics.

The reported lithium-sulfur batteries or lithium-sulfur flow batteries all have one or more of the following defects: the organic-inorganic composite solid electrolyte has low ionic conductivity at room temperature; the sulfide solid electrolyte is extremely unstable in contact with water and is easily decomposed. The preparation is difficult; the interface contact resistance with the positive and negative electrodes is large; the inorganic solid electrolyte is brittle and fragile, and it is not easy to form; the preparation steps are cumbersome, and it is not suitable for large-scale production.

In view of the above problems, the present invention designs and prepares an all-solid-state lithium-sulfur battery by using a lithiated sulfonic acid polymer solid electrolyte. The room temperature ionic conductivity of the lithiated sulfonic acid polymer membrane can be greater than 10 ^-5 S/cm, which can meet the requirements of lithium-sulfur batteries. The lithiated sulfonic acid polymer solid electrolyte used has the function of conducting lithium ions without complexing lithium salts. The positive electrode is made of active material sulfur or sulfur-containing compound, conductive additive and lithiated sulfonic acid polymer solid electrolyte mixed and ground evenly and then coated on the current collector. Among them, the conductive additive plays the role of conducting electrons, and the lithiated sulfonic acid polymer plays the role of conducting lithium ions. The negative electrode is metal lithium and lithium alloy. In order to avoid the strong reducibility of metallic lithium and improve the cycle performance of the battery, a separator can be added between the negative electrode and the polymer solid electrolyte separator. The positive electrode and the lithiated sulfonic acid polymer solid electrolyte are adhered together by hot pressing, and the positive electrode, the lithiated sulfonic acid polymer solid electrolyte, and the negative electrode are assembled into a battery by mechanical pressing. The all-solid-state lithium-sulfur battery designed by the invention can be applied to the fields of large-scale energy storage, electric vehicles, electric motorcycles, electric bicycles, portable electronic equipment, electric tools, uninterruptible power supplies, wearable equipment and the like.

All-solid-state lithium-sulfur batteries using lithiated sulfonic acid polymer solid electrolytes have not yet been reported.

SUMMARY OF THE INVENTION

The purpose of the present invention is to design an all-solid-state lithium-sulfur battery using a lithiated sulfonic acid polymer solid electrolyte to realize an all-solid-state lithium-sulfur secondary battery with high energy density, high safety, long life and low cost.

The invention is characterized in that the room temperature ionic conductivity of the lithiated sulfonic acid polymer film can be greater than 10 ^-5 S/cm, which can meet the requirements of lithium-sulfur batteries. The lithiated sulfonic acid polymer solid electrolyte used has the function of conducting lithium ions without complexing lithium salts. The positive electrode is made of active material sulfur or sulfur-containing compound, conductive additive and lithiated sulfonic acid polymer solid electrolyte mixed and ground evenly and then coated on the current collector. Among them, the conductive additive plays the role of conducting electrons, and the lithiated sulfonic acid polymer plays the role of conducting lithium ions. The negative electrode is metal lithium and lithium alloy. In order to avoid the strong reducibility of metallic lithium and improve the cycle performance of the battery, a separator can be added between the negative electrode and the polymer solid electrolyte separator. The positive electrode and the lithiated sulfonic acid polymer solid electrolyte are adhered together by hot pressing, and the positive electrode, the lithiated sulfonic acid polymer solid electrolyte, and the negative electrode are assembled into a battery by mechanical pressing. The all-solid-state lithium-sulfur battery designed by the invention can be applied to the fields of large-scale energy storage, electric vehicles, electric motorcycles, electric bicycles, portable electronic equipment, electric tools, uninterruptible power supplies, wearable equipment and the like.

The specific preparation process of the lithiated sulfonic acid polymer solid electrolyte membrane is as follows: put the sulfonic acid polymer electrolyte membrane into a LiOH solution with a concentration of 0.1-2 mol/L, and soak it at 20-100° C. for 0.5-96 hours , and then washed with the solvent of LiOH solution for 3 to 10 times to remove LiOH on the surface of the membrane, then dried at 65 to 120 °C for 1 to 6 hours, and then vacuum dried at 40 to 100 °C for 0.5 to 48 hours to obtain lithium sulfonic acid polymer membrane;

The sulfonic acid polymer solid electrolyte membrane can be a perfluorosulfonic acid-polytetrafluoroethylene film, a polytrifluorostyrene sulfonic acid film, a polydifluorostyrene sulfonic acid film, a polyaryl ether ketone sulfonic acid film, a poly One or more of imidesulfonic acid membrane and sulfonated polysulfone membrane;

The solvent of the LiOH solution can be one or more of water, methanol, ethanol, dimethyl sulfoxide, tetrahydrofuran, acetonitrile, dimethyl carbonate, and diethyl carbonate.

The active material of the sulfur positive electrode can be elemental sulfur or sulfide;

The elemental sulfur can be one or more of orthogonal sulfur, monoclinic sulfur, orthorhombic sulfur, elastic sulfur, and polymeric sulfur;

The sulfide can be inorganic metal sulfide or inorganic metal sulfur-selenium compound or inorganic metal sulfur-tellurium compound or sulfur-selenium solid solution S _x Se _1-x (0<x<1) or sulfur-tellurium solid solution S _x Te _{1 -x} (0<x<1) or one or more mixtures of organic sulfides or vulcanized polymers;

The cation of the inorganic metal sulfide can be Fe ²⁺ , Fe ³⁺ , Ni ²⁺ , Ni ³⁺ , Ti ⁴⁺ , Cu ⁺ , Cu ²⁺ , Co ²⁺ , W ⁴⁺ , Mo ⁴⁺ , one or more of Zn ²⁺ , Cd ²⁺ , Li ⁺ ;

The inorganic metal sulfur-selenide compound may be M(S _x Se _1-x ) ₂ (one or more of M=Ge, Mo, Co, Sn, Ta) (0<x<1) , MY(S _x Se _1-x ) ₂ (M=Cu, Ag, Li, Tl; one or more of Y=Ga, Al, Sb, In, Zn) (0<x<1), Cu ₂ Zn(S _x Se _1-x ) ₄ (0<x<1), Cu ₂ FeSn(S _x Se _1-x ) ₄ (0<x<1), CuInP ₂ (S _x Se _1-x ) One or more of ₆ (0<x<1), Cu ₂ (Zn _y Fe _1-y )Sn(S _x Se _1-x ) ₄ (0<x<1, 0<y<1) ;

The inorganic metal sulfur-tellurium compound can be Pb _1-y (S _x Te _1-x ) _y (0<x<1, 0<y<1), CuIn(S _x Te _1-x ) (0 <x<1), one or more of Ag ₉ FeTe ₂ S ₄ or Ag ₁₆ FeBiTe ₃ S ₈ or Ag ₆ TeS ₂ or Ag ₈ SnTe ₂ S ₄ ;

Wherein the organic sulfide can be one or more of thiol, thiophenol, thioether, dimercapto sulfide, polysulfide, and vulcanized polymer;

The vulcanized polymer can be one or more of vulcanized polyacrylonitrile, vulcanized polypyrrole, vulcanized polythiophene, vulcanized polyparaphenylene, vulcanized polyphenylacetylene, vulcanized polyaniline, vulcanized polyphenylene sulfide .

The conductive agent can be one or more of acetylene black, BALCK PEARLS 2000, Ketjen carbon black, Super-P, carbon nanotube, carbon nanofiber, activated carbon, and graphene;

The preparation method of the sulfur positive electrode is to mix the lithiated sulfonic acid polymer emulsion with sulfur or sulfide, a conductive agent and a solvent, and then mix them uniformly by stirring or ball milling to prepare a slurry. The solid content of the slurry is: 5% to 50%, and then use screen printing or spraying or coating or transfer coating to coat the slurry on one or both sides of the positive electrode current collector or coat it on the lithiated sulfonic acid polymer solid one side surface of the electrolyte separator;

The lithiated sulfonic acid polymer emulsion is prepared by dissolving the lithiated sulfonic acid polymer solid electrolyte membrane in a solvent at 20 to 100° C. The mass concentration of the lithiated sulfonic acid polymer is 1% to 100°C. 50%;

The solvent used in the sulfonic acid polymer emulsion and slurry is N-methylpyrrolidone, N,N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, diphenyl ether, hexamethylene One or more of methylphosphonide triamide and hexaethylphosphonide triamide;

The positive electrode current collector is aluminum foil or copper foil or carbon-coated aluminum foil or foamed nickel or foamed copper.

The mass ratio of sulfur or sulfide and conductive agent in the sulfur positive electrode is 1:9 to 19:1;

The mass ratio of sulfur or sulfide to lithiated sulfonic acid polymer in the sulfur positive electrode is 1:9-9:1.

Wherein the lithium alloy can be one or more metals selected from lithium and Mg, Ca, Al, Si, Ge, Sn, Pb, As, Sb, Bi, Pt, Ag, Au, Zn, Cd, and Hg The alloy, the mass content of lithium in the alloy is 10%-95%.

There is no protective layer or can be provided with a protective layer between the lithium or lithium alloy negative electrode and the solid electrolyte separator, and the protective layer can be composed of lithium phosphorus oxygen nitrogen, lithium silicon phosphorus oxygen nitrogen, lithium phosphate, lithium vanadium silicon oxygen, lithium carbonate , Lithium nitride, Lithium borohydride, Lithium titanate, Amorphous carbon in one or more composition.

The preparation method of the separator between the lithium negative electrode and the solid electrolyte separator is as follows: using a lithium ribbon or a lithium alloy ribbon or a lithiated sulfonic acid polymer solid electrolyte separator as a substrate, and using magnetron sputtering deposition or pulsed laser deposition or vacuum heating It is prepared by depositing a protective layer on the surface of the substrate by one or more of evaporation technology or electrostatic spray deposition or blade coating or sol-gel method.

The sulfur positive electrode coated on the surface of one side of the positive electrode current collector and the lithiated sulfonic acid polymer solid electrolyte separator are adhered together by hot pressing; the hot pressing temperature of the sulfur positive electrode and the lithiated sulfonic acid polymer solid electrolyte is: 80-240℃, the pressure is 0.5-5MPa.

The way of assembling the battery is mechanical compression; the outer packaging is one of aluminum-plastic film flexible packaging or aluminum shell or steel shell; the shape is button-shaped, cylindrical or square.

All-solid-state lithium-sulfur batteries can be used in large-scale energy storage, electric vehicles, electric motorcycles, electric bicycles, portable electronic devices, power tools, uninterruptible power supplies, wearable devices and other fields.

The advantages of the present invention are:

1. Compared with the lithium-sulfur battery using organic electrolyte, the all-solid-state lithium-sulfur battery using lithiated sulfonic acid polymer electrolyte does not have the shuttle effect caused by the dissolution of polysulfides, which avoids the corrosion of the metal lithium negative electrode and improves the performance. The Coulombic efficiency and cycle life of the battery; and there is no safety hazard caused by the flammability and leakage of the electrolyte, which improves the safety of the battery. It is not necessary to encapsulate the liquid, and it can be manufactured in a large area in a roll-to-roll method to improve production efficiency.

2. Compared with the all-solid-state lithium-sulfur battery using an inorganic solid electrolyte, the sulfonic acid polymer electrolyte has a lighter specific gravity (~2 g/cm ³ ), and it is easy to obtain an all-solid-state lithium-sulfur battery with a higher specific energy. The use of polymer emulsions to prepare sulfur positive electrode sheets can construct an efficient "sulfur (active material)/carbon (electrode)/solid electrolyte" interface inside the electrode, improve the activity of the sulfur electrode, and obtain batteries with excellent performance; Some pole piece coating processes and equipment are conducive to large-scale production. In addition, the sulfonic acid polymer electrolyte is easy to form a film, has good viscoelasticity, good compatibility with positive and negative electrodes, low interface contact resistance, and easy battery assembly; high elastic modulus, easy to process into various shapes, to meet a variety of occasions Use the requirements for the battery shape.

3. Compared with the inorganic-organic composite solid electrolyte, the lithiated sulfonic acid polymer solid electrolyte itself can conduct lithium ions without complexing lithium salts, and the preparation method is simple. It overcomes the disadvantage of using some lithium salts that are unstable in contact with water and oxygen, such as LiTFSi, which requires harsh electrode preparation environment. Moreover, the ionic conductivity of the lithiated sulfonic acid polymer solid electrolyte at room temperature is >10 ^-5 S/cm, which is better than that of the inorganic-organic composite solid electrolyte, which is generally lower than 10 ^-5 S/cm at room temperature.

Description of drawings

FIG. 1 is a schematic structural diagram of an all-solid-state lithium-sulfur battery using a lithiated sulfonic acid polymer solid electrolyte. 1 is the surface-protected metal lithium, 2 is the lithiated sulfonic acid polymer film, and 3 is the positive electrode of the all-solid-state lithium-sulfur battery.

2 is a charge-discharge curve of an all-solid-state lithium-sulfur battery using a lithiated sulfonic acid polymer solid electrolyte, and the all-solid-state lithium-sulfur battery is manufactured from the positive and negative electrode materials of Example 1.

3 is a cycle stability curve of an all-solid-state lithium-sulfur battery using a lithiated sulfonic acid polymer solid electrolyte, and the all-solid-state lithium-sulfur battery is manufactured from the positive and negative electrode materials of Example 1.

Detailed ways

The following examples are only to further illustrate the present invention, and the present invention should not be limited to the specific and explicit contents of the following examples without violating the gist of the present invention.

Example 1

The perfluorosulfonic acid-polytetrafluoroethylene membrane was soaked in 1M LiOH aqueous solution at 80°C for 12 hours, then washed with solvent for 3 to 10 times to remove LiOH on the surface of the membrane, and then dried at 100°C for 2 hours. Vacuum dried at 60 degrees for 48 hours to obtain a lithiated perfluorosulfonic acid-polytetrafluoroethylene membrane. Using NMP as solvent, the lithiated perfluorosulfonic acid-polytetrafluoroethylene polymer emulsion with a mass fraction of 5% was prepared at 80 °C. The positive active material sulfurized polyacrylonitrile, acetylene black, and lithiated perfluorosulfonic acid-polytetrafluoroethylene polymer were weighed in a mass ratio of 6:2:2, mixed and ground with NMP as a solvent, and then coated on aluminum foil. Then, dried in a vacuum oven at 55 °C overnight to obtain a sulfur cathode. The lithiated perfluorosulfonic acid-polytetrafluoroethylene membrane and the sulfur cathode were hot-pressed at 120 °C and 0.5 MPa for 3 min to obtain an integrated cathode and solid electrolyte membrane. The lithium metal sheet with a lithium nitride protective layer on one surface, the integrated positive electrode and the solid electrolyte membrane were assembled into a battery as shown in Figure ¹ , and then packaged in a button battery case, and the battery was tested at a current density of 90 μA/cm Constant current discharge, charge and discharge voltage range is 1-3V. The specific capacity of the battery calculated by the mass of sulfur is 1200mAh/g, and the capacity retention rate after 80 cycles is 62%.

Example 2

The polytrifluorostyrene sulfonic acid membrane was soaked in DMSO solution of 2M LiOH at 100°C for 12 hours, then washed with solvent for 3 to 10 times to remove LiOH on the surface of the membrane, and then dried by blasting at 100°C for 6 hours. Then vacuum drying at 100 degrees for 48 hours to obtain a lithiated polytrifluorostyrene sulfonic acid film. Using DMF as solvent, the lithiated polytrifluorostyrene sulfonic acid polymer emulsion with a mass fraction of 10% was prepared at 60 °C. The positive active material iron sulfide, Super-P, and lithiated polytrifluorostyrene sulfonic acid polymer were weighed in a mass ratio of 5:1:4, mixed and ground with DMF as a solvent, and then coated on carbon-coated aluminum foil. , dried in a vacuum oven at 55°C overnight to obtain a sulfur cathode. The lithiated polytrifluorostyrene sulfonic acid membrane and the sulfur cathode were hot-pressed at 110 °C and 1 MPa for 3 min to obtain an integrated cathode and solid electrolyte. The lithium metal with lithium borohydride protective layer on one surface, the integrated positive electrode and solid electrolyte are assembled into a battery as shown in Figure 1, and then packaged in a button battery case, and the battery is subjected to constant current at a current density of 90 μA/cm ² . Discharge, the charge and discharge voltage range is 1-3V. The specific capacity of the battery calculated by the mass of iron sulfide is 800mAh/g.

Example 3

The polydifluorostyrene sulfonic acid membrane was soaked in a mixed solution of 1M LiOH ethanol and water (volume ratio 1:1) at 80 °C for 12 hours, and then washed with solvent for 3 to 10 times to remove LiOH on the surface of the membrane. Blast drying at 80 degrees for 6 hours, and then vacuum drying at 40 degrees for 48 hours to obtain a lithiated polydifluorostyrene sulfonic acid membrane. Using DMAc as solvent, the lithiated polydifluorostyrene sulfonic acid polymer emulsion with a mass fraction of 4% was prepared at 90°C. The positive active material sublimed sulfur selenium solid solution, Ketjen carbon black, and lithiated polydifluorostyrene sulfonic acid polymer were weighed in a mass ratio of 4:3:3, mixed and ground with DMAc as a solvent, and then coated on copper. foil and dried in a vacuum oven at 55°C overnight. The lithiated polydifluorostyrene sulfonic acid membrane and the sulfur cathode were hot-pressed at 100 °C and 2 MPa for 3 min to obtain an integrated cathode and solid electrolyte. The lithium metal with a protective layer of lithium carbonate on one side, the integrated positive electrode and solid electrolyte were assembled into a battery as shown in Figure 1, and then packaged in a button battery case, and the battery was discharged at a constant current density of 90 μA/cm ² . , the charge and discharge voltage range is 1.5-3V. The specific capacity of the battery is calculated as 600mAh/g based on the mass of sulfur and selenium solid solution.

Example 4

The polyaryletherketonesulfonic acid membrane was soaked in 1M LiOH acetonitrile solution at 78°C for 12 hours, then washed with solvent for 3 to 10 times to remove the LiOH on the surface of the membrane, and then air-dried at 80°C for 2 hours. Vacuum dried at 50 degrees for 48 hours to obtain a lithiated polydifluorostyrene sulfonic acid membrane. Using diphenyl ether as solvent, a lithiated polyaryletherketonesulfonic acid polymer emulsion with a mass fraction of 4% was prepared at 100°C. The positive active material silver sulfur telluride, carbon nanotubes, and lithiated polyaryletherketonesulfonic acid polymer solid electrolyte were weighed in a mass ratio of 4:3:3, mixed and ground with diphenyl ether as a solvent, and then coated On the foamed copper, dry it in a vacuum oven at 55°C overnight to obtain a sulfur positive electrode. The lithiated polyaryl ether ketone sulfonic acid membrane and the sulfur cathode were hot-pressed at 115 °C and 1 MPa for 3 min to obtain an integrated cathode and solid electrolyte. The lithium metal and lithium-integrated cathode and solid electrolyte are assembled into a battery as shown in Figure 1, and then packaged in a button battery case. The battery is discharged at a constant current density of 90 μA/cm ² , and the charge-discharge voltage range is 1.5-3V. . The specific capacity of the battery calculated by the mass of silver sulfide telluride is 600mAh/g.

Example 5

The polyimide sulfonic acid membrane was soaked in 1M LiOH dimethyl carbonate solution at 80°C for 48 hours, then washed with solvent for 3 to 10 times to remove the LiOH on the surface of the membrane, and then air-dried at 80°C for 6 hours, and then vacuum-dried at 60 degrees for 48 hours to obtain a lithiated polyimide sulfonic acid membrane. The lithiated polyimide sulfonic acid polymer emulsion with a mass fraction of 10% was prepared at 50°C using hexamethylphosphonide triamide as solvent. The positive active material Co(S _x Se _1-x ) ₂ , carbon nanotubes, and lithiated polyimide sulfonic acid polymer solid electrolyte were weighed in a mass ratio of 4:3:3, and hexamethylphosphonyl Triamine was mixed and ground as a solvent, and then coated on foam nickel, and dried in a vacuum oven at 55°C overnight to obtain a sulfur positive electrode. The lithiated polyimide sulfonic acid membrane and the sulfur cathode were hot-pressed at 240 °C and 1 MPa for 3 min to obtain an integrated cathode and solid electrolyte. The lithium-aluminum alloy, the integrated positive electrode and the solid electrolyte were assembled into a battery as shown in Figure 1 and then encapsulated in a button battery case. The battery was discharged at a constant current density of 90 μA/cm ² , and the charge-discharge voltage range was 1.5-3V. . The specific capacity of the battery calculated by the mass of Co(S _x Se _1-x ) ₂ is 450 mAh/g.

Example 6

The sulfonated polysulfone membrane was soaked in 1M LiOH diethyl carbonate solution at 80°C for 12 hours, then washed with solvent for 3 to 10 times to remove LiOH on the surface of the membrane, and then dried by blasting at 80°C for 6 hours. Then vacuum-drying at 40 degrees for 48 hours to obtain a lithiated sulfonated polysulfone membrane. A 2% lithiated sulfonated polysulfone polymer emulsion was prepared at 75°C using hexaethylphosphonide triamide as solvent. The positive active material sulfide, carbon nanotubes, and lithiated sulfonated polysulfone polymer solid electrolyte were weighed in a mass ratio of 4:3:3, mixed and ground with hexaethylphosphine triamide as a solvent, and then coated. Covered on carbon-coated aluminum foil, dried in a vacuum oven at 55°C overnight to obtain a sulfur positive electrode. The lithiated sulfonated polysulfone membrane and the sulfur cathode were hot-pressed at 120 °C and 1 MPa for 3 min to obtain an integrated cathode and solid electrolyte. The lithium-silicon alloy, the integrated positive electrode and the solid electrolyte were assembled into a battery as shown in Figure 1 and then packaged in a button battery case. The battery was discharged at a constant current density of 90 μA/cm ² , and the charge-discharge voltage range was 1.5-3V. . The specific capacity of the battery was calculated as 800mAh/g based on the mass of sulfide.

Claims (10)

1. a kind of all solid state lithium-sulfur cell, it is characterised in that: all solid lithium sulphur battery include sulphur anode, lithium or lithium alloy cathode with And the sulfonic acid polymer solid electrolyte diaphragm of lithiumation；Solid electrolyte diaphragm be located at sulphur anode and lithium or lithium alloy cathode it Between；Sulphur anode includes the sulfonic acid polymer of sulfur-bearing active material, conductive agent and lithiumation；Sulphur anode, the sulfonic acid polymer of lithiumation are solid Body electrolyte, lithium or lithium alloy cathode, which successively overlap, is assembled into battery；

The mass ratio of elemental sulfur or sulfide and conductive agent in the sulphur anode is 1:9 ~ 19:1；

The mass ratio of elemental sulfur or sulfide and the sulfonic acid polymer of lithiumation in the sulphur anode is 1:9 ~ 9:1；

The preparation method of the sulphur anode is by the sulfonic acid polymer lotion of lithiumation and elemental sulfur or sulfide, conductive agent and molten It is mixed in the way of stirring or ball milling after agent mixing, is made slurry, the solid content of slurry is 5% ~ 50%, then using screen printing Brush or spraying or coating mode by slurry be coated in plus plate current-collecting body one or both sides surface or coated in the sulfonic acid of lithiumation One side surface of copolymer solid electrolyte diaphragm；

The sulfonic acid polymer lotion of the lithiumation is the sulfonic acid polymer solid electrolyte diaphragm of the lithiumation 20 ~ 100 It is dissolved under the conditions of DEG C made of solvent, the mass concentration of the sulfonic acid polymer of lithiumation is 1% ~ 50%.

2. all solid state lithium-sulfur cell according to claim 1, it is characterized in that: above-mentioned coating is transfer coated.

3. all solid state lithium-sulfur cell according to claim 1, it is characterized in that: the sulfonic acid polymer solid electricity of the lithiumation Solve the specific preparation process of matter diaphragm are as follows: sulfonic acid polymer solid electrolyte film is put into the LiOH that concentration is 0.1 ~ 2 mol/L In solution, is impregnated 0.5 ~ 96 hour at 20 ~ 100 DEG C, then washed 3 ~ 10 times with the solvent of LiOH solution, remove film surface LiOH, then at 65 ~ 120 DEG C air blast dry 1 ~ 6 hour, after be dried in vacuo 0.5 ~ 48 hour at 40 ~ 100 DEG C again, obtain The sulfonic acid polymer solid electrolyte diaphragm of lithiumation；

The sulfonic acid polymer solid electrolyte film is perfluorinated sulfonic acid-polytetrafluoroethylene film, polytriflurostyrene sulphonic film, gathers One of difluoro styrene sulfonic acid film, poly(aryl ether ketone) sulfonate film, polyimides sulfonate film, sulfonated polysulfone membrane or two kinds or more；

The solvent of the LiOH solution is water, methanol, ethyl alcohol, dimethyl sulfoxide, tetrahydrofuran, acetonitrile, dimethyl carbonate, two One of ethyl carbonate ester or two kinds or more.

4. all solid state lithium-sulfur cell according to claim 1, it is characterized in that: the elemental sulfur or sulfide are sulphur anode Active material；

The elemental sulfur is one of rhombic sulfur, monoclinic sulphur, rhombic sulfur, elastic sulfur, polymerised sulphur or two kinds or more；

The sulfide is the sulphur selenium compound of inorganic metal sulfide or inorganic metal or the sulphur tellurium compound of inorganic metal Or sulphur selenium solid solution S_xSe_1-x, 0 < x < 1 or sulphur tellurium solid solution S_xTe_1-x, one of 0 < x < 1 or organic sulfur compound or two kinds or more Mixture；

Wherein the cation of the inorganic metal sulfide is Fe²⁺、Fe³⁺、Ni²⁺、Ni³⁺、Ti⁴⁺、Cu⁺、Cu²⁺、Co²⁺、W⁴⁺、 Mo⁴⁺、Zn²⁺、Cd²⁺、Li⁺One of or two kinds or more；

Wherein the sulphur selenium compound of the inorganic metal is M (S_xSe_1-x)₂, wherein 0 < x < 1, M=Ge, Mo, Co, Sn, Ta One of or two kinds or more, MY (S_xSe_1-x)₂, wherein 0 < x < 1, M=Cu, Ag, Li, Tl;In Y=Ga, Al, Sb, In, Zn One or two or more kinds of, Cu₂Zn(S_xSe_1-x)₄, 0 < x < 1, Cu₂FeSn(S_xSe_1-x)₄, 0 < x < 1, CuInP₂(S_xSe_1-x)₆, 0 < x < 1 、Cu₂(Zn_yFe_1-y)Sn(S_xSe_1-x)₄, wherein 0 < x < 1, one of 0 < y < 1 or two kinds or more；

Wherein the sulphur tellurium compound of the inorganic metal is Pb_1-y(S_xTe_1-x)_y, wherein 0 < x < 1,0 < y < 1, CuIn (S_xTe_1-x), 0 < x < 1, Ag₉FeTe₂S₄Or Ag₁₆FeBiTe₃S₈Or Ag₆TeS₂Or Ag₈SnTe₂S₄One of or two kinds or more；

Wherein the organic sulfur compound be mercaptan, thiophenol, thioether, dimercapto sulfide, polysulfide, in sulfide polymer It is one or two or more kinds of；

Wherein the sulfide polymer is sulfurized polyacrylonitrile, vulcanization polypyrrole, vulcanization polythiophene, vulcanizes and gather to benzene, vulcanization Polyphenylacetylene, vulcanization polyaniline, vulcanization one of polyphenylene sulfide or two kinds or more.

5. all solid state lithium-sulfur cell according to claim 1, it is characterized in that: the conductive agent is acetylene black, BLACK One of PEARLS 2000, section's qin carbon black, Super-P, carbon nanotube, carbon nano-fiber, active carbon, graphene or two kinds More than.

6. all solid state lithium-sulfur cell according to claim 1, it is characterized in that:

Solvent used in sulfonic acid polymer lotion and slurry described in wherein is N-Methyl pyrrolidone, N, N- dimethyl formyl One of amine, dimethyl acetamide, dimethyl sulfoxide, diphenyl ether, sub-phosphono triamine, Hexaethyl Asia phosphono triamine or Two kinds or more；

The plus plate current-collecting body is aluminium foil or copper foil or carbon-coated aluminum foils or nickel foam or foam copper.

7. all solid state lithium-sulfur cell according to claim 1, it is characterized in that: wherein the lithium alloy be lithium and Mg, Ca, The alloy of one of Al, Si, Ge, Sn, Pb, In, Sb, Bi, Fe, Se, Ag, Au, Zn, Cd, Hg or two kinds or more metal, alloy The mass content of middle lithium is 10%-95%.

8. all solid state lithium-sulfur cell according to claim 1, it is characterized in that: wherein the lithium or lithium alloy cathode with it is upper State between solid electrolyte diaphragm unprotect layer or be equipped with protective layer, protective layer by LiPON, lithium silicon phosphorous oxynitride, lithium phosphate, One of lithium vanadium silicon oxygen, lithium carbonate, lithium nitride, lithium borohydride, lithium titanate, amorphous carbon or two kinds of composition described above.

9. all solid state lithium-sulfur cell according to claim 8, it is characterized in that: lithium or lithium alloy cathode and above-mentioned solid electrolytic Protective layer between matter diaphragm the preparation method comprises the following steps: with lithium piece or lithium alloy piece or the sulfonic acid polymer solid electrolyte of lithiumation every Film is substrate, deposited using magnetron sputtering deposition or pulse laser deposition or vacuum thermal evaporation technology or electrostatic spray or blade coating or One of sol-gal process or two kinds or more are prepared in one side surface of substrate deposition protective layer.

10. all solid state lithium-sulfur cell according to claim 7, it is characterized in that: it is coated in plus plate current-collecting body one or both sides The sulphur anode on surface and the sulfonic acid polymer solid electrolyte diaphragm of lithiumation are adhered to integral by hot pressing mode；Sulphur anode and lithium The hot-pressing processing temperature of the sulfonic acid polymer solid electrolyte of change is 80-240 DEG C, pressure 0.5-5MPa.