PRE-LITHIATED POLYPHENYLENE SULFIDE, POLYPHENYLENE SULFIDE-BASED SOLID ELECTROLYTE MEMBRANE, BATTERY ELECTRODE SHEET, QUASI-SOLID-STATE LITHIUM ION BATTERY AND METHOD FOR MANUFACTURING SAME

Abstract

A method for manufacturing a pre-lithiated polyphenylene sulfide with a high solid solubility of lithium includes: placing NMP, Li.sub.2S, and LiOH into a high-pressure reactor to obtain a mixture, and heating the mixture to 150-250° C. for a high-temperature dehydration for 2-5 h, and then cooling the mixture to 100° C. and adding p-DCB to the mixture for a reaction at 150-250° C. for 80-200 min; dropwise adding hydrochloric acid in an identical amount as that of the LiOH neutralize LiOH, and removing NMP and H.sub.2O by evaporation or sublimation, to obtain a dry mixed powder; and to the dry mixed powder, adding a chloride ion complexing agent to obtain a mixture, stirring the mixture to homogeneity, and placing the mixture in a sealed reactor for a reaction at 150-250° C. for 80-200 min, followed by washing and drying, to obtain the pre-lithiated polyphenylene sulfide.

Claims

1. A method for manufacturing a pre-lithiated polyphenylene sulfide with a high solid solubility of lithium, comprising the following steps: placing N-methylpyrrolidone (NMP), lithium sulfide (Li.sub.2S), and lithium hydroxide (LiOH) into a high-pressure reactor with a stirring function to obtain a first mixture, and heating the first mixture to 150-250° C. for a high-temperature dehydration for 2-5 h, and then cooling the first mixture to 100° C. and adding 1,4-dichlorobenzene (p-DCB) to the first mixture for a first reaction at 150-250° C. for 80-200 min; dropwise adding hydrochloric acid in an identical amount as an amount of the LiOH on a molar basis to neutralize the LiOH, and removing the NMP and H.sub.2O by an evaporation or sublimation, to obtain a dry mixed powder; and to the dry mixed powder, adding a chloride ion complexing agent to obtain a second mixture, stirring the second mixture to homogeneity, and placing the second mixture in a sealed reactor for a second reaction at 150-250° C. for 80-200 min, followed by washing and drying, to obtain the pre-lithiated polyphenylene sulfide with the high solid solubility of lithium.

2. The method for manufacturing the pre-lithiated polyphenylene sulfide according to claim 1, wherein the Li.sub.2S is formed by a high-temperature reaction of a lithium metal powder with a sulfur powder or the Li.sub.2S is formed by a carbothermal reduction reaction of lithium sulfate (Li.sub.2SO.sub.4).

3. The method for manufacturing the pre-lithiated polyphenylene sulfide according to claim 1, wherein the NMP, the Li.sub.2S, and the LiOH are at a molar ratio of 1-5:1:0.05-0.2.

4. The method for manufacturing the pre-lithiated polyphenylene sulfide according to claim 1, wherein the Li.sub.2S and the p-DCB are at a molar ratio of 1.3-0.8:1.

5. The method for manufacturing the pre-lithiated polyphenylene sulfide according to claim 1, wherein the evaporation or sublimation comprises a hot-air drying method, a rotary evaporation method, and a freeze-drying method, to maximize a retention of solid-phase components and only remove the NMP and the H.sub.2O.

6. The method for manufacturing the pre-lithiated polyphenylene sulfide according to claim 1, wherein the chloride ion complexing agent is an organic metal-ion-free complexing agent, and the chloride ion complexing agent is preferably calixcrown ether, caliximidazole, calixpyrrole, or calixarene.

7. The method for manufacturing the pre-lithiated polyphenylene sulfide according to claim 1, wherein the chloride ion complexing agent is added in an amount on the molar basis, wherein the amount of the chloride ion complexing agent is 0.01-0.2 times an amount of the p-DCB.

8. (canceled)

9. A pre-lithiated polyphenylene sulfide prepared by the method according to claim 1.

10. A method for preparing an isotropic polyphenylene sulfide-based solid electrolyte membrane, comprising the following steps: mixing a pre-lithiated polyphenylene sulfide powder and polytetrafluoroethylene (PTFE) uniformly in a mixer under a temperature condition where the PTFE is in a glassy state, to obtain a mixed powder, and air-grinding the mixed powder with a supersonic gas to allow a molecular chain of the PTFE to extend and open and form a physical adhesion with the pre-lithiated polyphenylene sulfide powder, without a chemical reaction; then removing the supersonic gas in the mixed powder through an extruder to form a continuous cake-like wide strip, followed by hot pressing the continuous cake-like wide strip into a pre-lithiated polyphenylene sulfide membrane material with a hot roll at a temperature lower than 150° C., and winding the pre-lithiated polyphenylene sulfide membrane material up; and preparing the isotropic polyphenylene sulfide-based solid electrolyte membrane.

11. (canceled)

12. (canceled)

13. The method for preparing the isotropic polyphenylene sulfide-based solid electrolyte membrane according to claim 10, wherein the pre-lithiated polyphenylene sulfide powder and the PTFE are mixed uniformly in the mixer at a temperature controlled below 10° C. for a mixing time of 0.5-4 h.

14. (canceled)

15. A polyphenylene sulfide-based solid electrolyte membrane prepared by the method according to claim 10.

16-26. (canceled)

27. The polyphenylene sulfide-based solid electrolyte membrane according to claim 15, wherein the pre-lithiated polyphenylene sulfide powder and the PTFE are mixed uniformly in the mixer at a temperature controlled below 10° C. for a mixing time of 0.5-4 h.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0050] FIG. 1 is a process flow chart of a method for manufacturing a quasi-solid-state lithium ion battery with a high safety and a high volumetric energy density as described in the present invention.

[0051] FIG. 2 is a schematic diagram of a perforated carbon-coated current collector.

[0052] FIG. 3 is a schematic diagram of a single-side-loaded electrode in which an electrode membrane is thermally laminated with a perforated carbon-coated current collector.

[0053] FIG. 4 is a structural representation of a laminate sheet layer with a “sandwich” structure.

[0054] FIG. 5 is a schematic diagram of a battery stack and impregnation channels for electrolyte solution.

[0055] FIG. 6 is a structural representation of a stack of 5 laminate sheet layers with “sandwich” structure.

[0056] FIG. 7A and FIG. 7B show charge/discharge curves of a LiNi.sub.0.5Co.sub.0.2Mn.sub.0.3O.sub.2/graphite quasi-solid-state battery at the room temperature of 25° C. and different current densities.

[0057] FIG. 8 is a cycle diagram of a LiNi.sub.0.5Co.sub.0.2Mn.sub.0.3O.sub.2/graphite quasi-solid-state battery at the room temperature of 25° C. and 1C.

[0058] FIG. 9A and FIG. 9B show charge/discharge curves of a LiCoO.sub.2/Li.sub.4Ti.sub.5O.sub.2 quasi-solid-state battery at the room temperature of 25° C. and different current densities.

[0059] In the figures:

[0060] 1—Perforated carbon—coated layer, 2—perforated current collector, 3—thick electrode membrane, 301—thick positive electrode membrane, 302—thick negative electrode membrane, 4—pre—lithiated polyphenylene sulfide—based solid electrolyte, and 5—electrolyte impregnation channel.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0061] In order to make the technical solutions of the present invention clearer, the technical solutions of the present invention will be described clearly and completely below. It is obvious that the examples described are part of the examples of the present invention, rather than all of them.

[0062] The quasi-solid-state lithium ion battery according to the present invention is composed of a laminate sheet layer with a “sandwich” structure. According to the design requirement for the battery capacity, the number of the sheet layers is determined and the sheet layers are stacked together. Two perforated current collectors attached form the impregnation paths for the electrolyte solution. The laminate sheet layer with the “sandwich” structure is formed by hot pressing a thick single-side-loaded positive electrode, a solid electrolyte, and a thick single-side-loaded negative electrode. The thick single-side-loaded positive electrode is prepared by a manufacturing method independent of a solvent, including preheating a variety of carbon materials, an electrode active material and PTFE in supersonic jet gas, performing PTFE directional drawing to allow the molecular chain of PTFE to extend and open, then forming a membrane through multi-step rolling, and finally laminating the membrane with the perforated carbon-coated current collector through hot pressing. The solid electrolyte is a pre-lithiated polyphenylene sulfide membrane material with a high solid solubility of lithium. The pre-lithiated polyphenylene sulfide powder with a high solid solubility of lithium and PTFE are subjected to jet-drawing with supersonic jet gas in an apparatus for PTFE directional drawing, and extruded to remove the gas to form a cake. After primary rolling and lamination rolling of multiple membranes, the pre-lithiated polyphenylene sulfide membrane material is prepared.

[0063] PTFE is selected as the polymer binder. Because the PTFE powder has a high compression ratio, a high molecular weight, and long chain segments, its molecular chain can quickly unfold and form a spatial network by grinding with supersonic air, to adhere and wrap the powder, which is conducive to the uniform distribution and adhesion of the powder, and is more conducive to film formation.

[0064] All the film formation steps in the process for manufacturing the quasi-solid-state lithium ion battery are independent of a solvent, which greatly simplifies the battery manufacturing process and makes the process more environmentally friendly. The solid solubility of lithium in the pre-lithiated polyphenylene sulfide-based solid electrolyte membrane material prepared is high, and chloride ions in the membrane material are effectively bound, thereby allowing the membrane material to be a good conductor of single lithium ions. The prepared battery electrode sheet does not rely on a solvent, and has a high loading, and a uniform and controllable thickness. The manufactured quasi-solid-state lithium ion battery has a simplified assembly process, and has characteristics of high safety, long lifetime, and high volumetric energy density, and the impregnation of the electrolyte solution is convenient, and it is easy to manufacture a blade battery with a large area and a low thickness.

[0065] The overall process flow of the method for manufacturing the quasi-solid-state lithium ion battery with a high safety and a high volumetric energy density according to the present invention is shown in FIG. 1 and will be explained below in detail in combination with examples.

Example 1

[0066] (1) Preparation of a pre-lithiated polyphenylene sulfide membrane material with a high solid solubility of lithium:

[0067] N-methylpyrrolidone (NMP), lithium sulfide (Li.sub.2S), and lithium hydroxide (LiOH) at a ratio of 3:1:0.1 on a molar basis were placed into a high-pressure reactor with a stirring function, and heated to 200° C. for high-temperature dehydration for 4 h, to obtain a dehydrated system. Secondly, the dehydrated system was cooled to 100° C., and 1,4-dichlorobenzene (p-DCB) was added at a ratio of p-DCB to Li.sub.2S of 1:1 on a molar basis. Reaction was allowed to proceed at 220° C. for 130 min, to obtain a mixed slurry. Thirdly, a predetermined amount of hydrochloric acid was added dropwise to the mixed slurry, where the amount of HCl was the same as that of LiOH on a molar basis, to exactly neutralize LiOH. NMP and H.sub.2O were removed from the mixed slurry by evaporation or sublimation, to obtain a dry mixed powder. To the mixed powder, calixcrown ether was added in an amount on a molar basis that is 0.17 time that of p-DCB, and stirred uniformly to obtain a mixture. The mixture was placed into a sealed reactor and kept at 210° C. for 160 min, to obtain a powder. Finally, the powder obtained from the above reaction was washed with deionized water under stirring for a predetermined period of time and then filtered, to obtain a filter cake. The filter cake was washed and dried again to obtain the pre-lithiated polyphenylene sulfide with a high solid solubility of lithium as the final product. The pre-lithiated polyphenylene sulfide powder and a PTFE powder were mixed at a weight percent ratio of 94%:6%, and PTFE in the mixture was subjected to jet-drawing in the apparatus for PTFE directional drawing with dry compressed air preheated at 50° C. with air flow rate reaching supersonic speed, to form a spatially reticulated loose micelle which then was collected. The powder was made into a continuous cake-like wide strip through an extruder, and then the continuous cake-like wide strip was subjected to lamination rolling several times through a hot roller press, to manufacture a membrane. The final thickness of the membrane material was 35 μm, and the lithium ion conductivity of the manufactured membrane material was 7*104 S.Math.cm.sup.−1.

[0068] (2) Preparation of a high-loading battery electrode sheet by a method independent of a solvent:

[0069] LiNi.sub.0.5Co.sub.0.2Mn.sub.0.3O.sub.2 as the positive electrode active material or graphite as the negative electrode active material was mixed uniformly with artificial graphite, activated carbon and acetylene black at a weight percent ratio of 86%:7%:5%:2% in a VC-type high-efficiency asymmetric mixer to obtain a powder A. In a low-temperature cold storage at 5° C., the polytetrafluoroethylene granular powder was mixed uniformly with the above mixed powder A at a weight percent ratio of 6%:94% in a V-type mixer for 2 h, to obtain a powder B. PTFE in the powder B was subjected to jet-drawing in the apparatus for PTFE directional drawing with dry compressed air preheated at 50° C. with air flow rate reaching supersonic speed, to form a spatially reticulated loose micelle which then was collected, to prepare a mixed powder C, and the ground mixed powder C was discharged with the air flow and collected. The mixed powder C was rolled twice through a hot roller press to form a membrane at a hot pressing temperature of 180° C. After the first rolling, the thickness of the positive electrode membrane was about 500 μm, and the thickness of the negative electrode membrane was about 300 μm. After the second rolling, the thickness of the positive electrode membrane was about 250 μm, and the thickness of the negative electrode membrane was about 120 μm. The positive electrode LiNi.sub.0.5Co.sub.0.2Mn.sub.0.3O.sub.2 membrane and the negative electrode graphite membrane were thermally laminated respectively onto one side of a perforated carbon-coated aluminum foil and perforated carbon-coated copper foil through a hot press lamination roll at a temperature of 160° C., to prepare a thick single-side-loaded LiNi.sub.0.5Co.sub.0.2Mn.sub.0.3O.sub.2 positive electrode, and a thick single-side-loaded graphite negative electrode, respectively.

[0070] The structure of the above perforated carbon-coated aluminum foil or perforated carbon-coated copper foil is shown in FIG. 2. The structure of the thick single-side-loaded LiNi.sub.0.5Co.sub.0.2Mn.sub.0.3O.sub.2 positive electrode and the thick single-side-loaded graphite negative electrode manufactured is shown in FIG. 3.

[0071] (3) Assembly of a quasi-solid-state lithium ion battery:

[0072] Using the thick single-side-loaded LiNi.sub.0.5Co.sub.0.2Mn.sub.0.3O.sub.2 positive electrode as a positive electrode sheet, and the thick single-side-loaded graphite negative electrode as a negative electrode sheet, the positive electrode sheet, the pre-lithiated polyphenylene sulfide membrane material with a high solid solubility of lithium, and the negative electrode sheet were stacked together sequentially, with the unloaded side of each of the current collectors of the positive electrode sheet and the negative electrode sheet facing outwards, followed by hot press lamination at 100° C. to form a laminate sheet layer with a “sandwich” structure, as shown in FIG. 4. Then, 5 laminate sheet layers with “sandwich” structure were stacked together by a stacking machine, as shown in FIGS. 5 and 6, where the aluminum current collectors of the positive electrodes were attached to each other, and the copper current collectors of the negative electrodes were attached to each other. The pore paths on the current collector and the gap between two current collectors formed electrolyte solution impregnation channels 5. The tab parts were welded and packaging was performed with an aluminum plastic film, followed by injecting a carbonate-based electrolyte solution inside the aluminum plastic film under vacuum and heat sealing the aluminum plastic film into a case. The charge/discharge curves of the quasi-solid-state battery at the room temperature of 25° C. and different current densities are shown in FIG. 7A and FIG. 7B. The cycle performance of the quasi-solid-state battery at 1 C is shown in FIG. 8, without capacity reduction after 500 cycles. No ignition or exploding occurred in the nail penetration test.

Example 2

[0073] (1) Preparation of a pre-lithiated polyphenylene sulfide membrane material with a high solid solubility of lithium:

[0074] N-methylpyrrolidone (NMP), lithium sulfide (Li.sub.2S), and lithium hydroxide (LiOH) at a ratio of 4:1:0.15 on a molar basis were placed into a high-pressure reactor with a stirring function, and heated to 200° C. for high-temperature dehydration for 4 h, to obtain a dehydrated system. Secondly, the dehydrated system was cooled to 100° C., and 1,4-dichlorobenzene (p-DCB) was added at a ratio of p-DCB to Li.sub.2S of 1:1.2 on a molar basis. Reaction was allowed to proceed at 220° C. for 130 min, to obtain a mixed slurry. Thirdly, a predetermined amount of hydrochloric acid was added dropwise to the mixed slurry, where the amount of HCl was the same as that of LiOH on a molar basis, to exactly neutralize LiOH. NMP and H.sub.2O were removed from the mixed slurry by evaporation or sublimation, to obtain a dry mixed powder. To the mixed powder, caliximidazole was added in an amount on a molar basis that is 0.05 time that of p-DCB, and stirred uniformly to obtain a mixture. The mixture was placed into a sealed reactor and kept at 210° C. for 160 min, to obtain a powder. Finally, the powder obtained from the above reaction was washed with deionized water under stirring for a predetermined period of time and then filtered, to obtain a filter cake. The filter cake was washed and dried again to obtain the pre-lithiated polyphenylene sulfide with a high solid solubility of lithium as the final product. The pre-lithiated polyphenylene sulfide powder and a PTFE powder were mixed at a weight percent ratio of 94%:6%, and PTFE in the mixture was subjected to jet-drawing in the apparatus for PTFE directional drawing with dry compressed air preheated at 50° C. with air flow rate reaching supersonic speed, to form a spatially reticulated loose micelle which then was collected. The powder was made into a continuous cake-like wide strip through an extruder, and then the continuous cake-like wide strip was subjected to lamination rolling several times through a hot roller press, to manufacture a membrane. The final thickness of the membrane material was 52 μm, and the lithium ion conductivity of the manufactured membrane material was 1*10.sup.−3 S.Math.cm.sup.−1.

[0075] (2) Preparation of a high-loading battery electrode sheet by a method independent of a solvent:

[0076] LiCoO.sub.2 as the positive electrode active material or Li.sub.4Ti.sub.5O.sub.12 as the negative electrode active material was mixed uniformly with artificial graphite, activated carbon and acetylene black at a weight percent ratio of 89%:6%:4%:1% in a VC-type high-efficiency asymmetric mixer to obtain a powder A. In a low-temperature cold storage at 5° C., the polytetrafluoroethylene granular powder was mixed uniformly with the above mixed powder A at a weight percent ratio of 6%:94% in a V-type mixer for 2 h, to obtain a powder B. PTFE in the powder B was subjected to jet-drawing in the apparatus for PTFE directional drawing with dry compressed air preheated at 50° C. with air flow rate reaching supersonic speed, to form a spatially reticulated loose micelle which then was collected, to prepare a mixed powder C, and the mixed powder C was rolled twice through a hot roller press to form a membrane at a hot pressing temperature of 180° C. After the first rolling, the thickness of the positive electrode membrane was about 450 μm, and the thickness of the negative electrode membrane was about 550 μm. After the second rolling, the thickness of the positive electrode membrane was about 220 μm, and the thickness of the negative electrode membrane was about 300 μm. An aluminum foil was used as the current collector, which was coated with carbon and perforated, as shown in FIG. 2. The positive electrode LiCoO.sub.2 membrane or the negative electrode Li.sub.4Ti.sub.5O.sub.2 membrane was thermally laminated onto one side of the perforated carbon-coated aluminum foil through a hot press lamination roll at a temperature of 160° C., as shown in FIG. 3, to prepare a thick single-side-loaded LiCoO.sub.2 positive electrode, or a thick single-side-loaded Li.sub.4Ti.sub.5O.sub.12 negative electrode.

[0077] (3) Assembly of a quasi-solid-state lithium ion battery:

[0078] Using the thick single-side-loaded LiCoO.sub.2 positive electrode as a positive electrode sheet, and the thick single-side-loaded LiTi.sub.5O.sub.12 negative electrode as a negative electrode sheet, the positive electrode sheet, the pre-lithiated polyphenylene sulfide membrane material with a high solid solubility of lithium, and the negative electrode sheet were stacked together sequentially, with the unloaded side of each of the current collectors of the positive electrode sheet and the negative electrode sheet facing outwards, followed by hot press lamination at 100° C. to form a laminate sheet layer with a “sandwich” structure, as shown in FIG. 4. Then, 10 laminate sheet layers with “sandwich” structure were stacked together by a stacking machine, where the aluminum current collectors of the positive electrodes were attached to each other, and the copper current collectors of the negative electrodes were attached to each other, as shown in FIGS. 5 and 6. The tab parts were welded and packaging was performed with an aluminum plastic film, followed by injecting a carbonate-based electrolyte solution inside the aluminum plastic film under vacuum and heat sealing the aluminum plastic film into a case. The charge/discharge curves of the quasi-solid-state battery at the room temperature of 25° C. and different current densities are shown in FIG. 9A and FIG. 9B. The capacity retention at 1 C was as high as 90%. The battery has an excellent rate performance.

Example 3

[0079] (1) Preparation of a pre-lithiated polyphenylene sulfide membrane material with a high solid solubility of lithium:

[0080] N-methylpyrrolidone (NMP), lithium sulfide (Li.sub.2S), and lithium hydroxide (LiOH) at a ratio of 5:1:0.18 on a molar basis were placed into a high-pressure reactor with a stirring function, and heated to 200° C. for high-temperature dehydration for 4 h, to obtain a dehydrated system. Secondly, the dehydrated system was cooled to 100° C., and 1,4-dichlorobenzene (p-DCB) was added at a ratio of p-DCB to Li.sub.2S of 1:0.9 on a molar basis. Reaction was allowed to proceed at 220° C. for 130 min, to obtain a mixed slurry.

[0081] Thirdly, a predetermined amount of hydrochloric acid was added dropwise to the mixed slurry, where the amount of HCl was the same as that of LiOH on a molar basis, to exactly neutralize LiOH. NMP and H.sub.2O were removed from the mixed slurry by evaporation or sublimation, to obtain a dry mixed powder. To the mixed powder, calixpyrrole was added in an amount on a molar basis that is 0.2 time that of p-DCB, and stirred uniformly to obtain a mixture. The mixture was placed into a sealed reactor and kept at 210° C. for 160 min, to obtain a powder. Finally, the powder obtained from the above reaction was washed with deionized water under stirring for a predetermined period of time and then filtered, to obtain a filter cake. The filter cake was washed and dried again to obtain the pre-lithiated polyphenylene sulfide with a high solid solubility of lithium as the final product. The pre-lithiated polyphenylene sulfide powder and a PTFE powder were mixed at a weight percent ratio of 94%:6%, and PTFE in the mixture was subjected to jet-drawing in the apparatus for PTFE directional drawing with dry compressed air preheated at 50° C. with air flow rate reaching supersonic speed, to form a spatially reticulated loose micelle which then was collected. The powder was made into a continuous cake-like wide strip through an extruder, and then the continuous cake-like wide strip was subjected to lamination rolling several times through a hot roller press, to manufacture a membrane. The final thickness of the membrane material was 37 μm, and the lithium ion conductivity of the manufactured membrane material was 8.2*10.sup.−4 S.Math.cm.sup.−1.

[0082] (2) Preparation of a high-loading battery electrode sheet by a method independent of a solvent:

[0083] LiNi.sub.1.5Mn.sub.0.5O.sub.4 as the positive electrode active material or Li.sub.4Ti.sub.5O.sub.12 as the negative electrode active material was mixed uniformly with artificial graphite, activated carbon and acetylene black at a weight percent ratio of 89%:6%:4%:1% in a VC-type high-efficiency asymmetric mixer to obtain a powder A. In a low-temperature cold storage at 5° C., the polytetrafluoroethylene granular powder was mixed uniformly with the above mixed powder A at a weight percent ratio of 6%:94% in a V-type mixer for 2 h, to obtain a powder B. PTFE in the powder B was subjected to jet-drawing in the apparatus for PTFE directional drawing with dry compressed air preheated at 50° C. with air flow rate reaching supersonic speed, to form a spatially reticulated loose micelle which then was collected, to prepare a mixed powder C. The mixed powder C was rolled twice through a hot roller press to form a membrane at a hot pressing temperature of 150° C. After the first rolling, the thickness of the positive electrode membrane was about 500 μm, and the thickness of the negative electrode membrane was about 500 μm. After the second rolling, the thickness of the positive electrode membrane was about 280 μm, and the thickness of the negative electrode membrane was about 280 μm. The positive electrode graphite membrane was thermally laminated onto one side of the perforated carbon-coated aluminum foil at a thermal lamination rolling temperature of 160° C.

[0084] (3) Assembly of a quasi-solid-state lithium ion battery:

[0085] The solvent-independent high-loading battery LiNi.sub.1.5Mn.sub.0.5O.sub.4 single-side-loaded positive electrode sheet, Li.sub.4Ti.sub.5O.sub.12 negative electrode, and the pre-lithiated polyphenylene sulfide membrane material with a high solid solubility of lithium were stacked together, with the loaded sides of the positive and negative electrodes being separated by the membrane material and the unloaded sides of the current collectors being facing outwards, followed by hot press lamination at 110° C. to form a laminate sheet layer with a “sandwich” structure, as shown in FIG. 4. Then, 15 laminate sheet layers with “sandwich” structure were stacked together by a stacking machine, where the aluminum current collectors of the positive electrodes were attached to each other, and the copper current collectors of the negative electrodes were attached to each other. The tab parts were welded and packaging was performed with an aluminum plastic film, followed by injecting an ionic liquid electrolyte solution containing LiTFSI and FEC inside the aluminum plastic film under vacuum and heat sealing the aluminum plastic film into a case, to manufacture a high-pressure lithium titanate quasi-solid-state lithium ion battery.