WO2020244333A1 - Nouvelle batterie à semi-conducteur et matériau d'électrode positive associé - Google Patents

Nouvelle batterie à semi-conducteur et matériau d'électrode positive associé Download PDF

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WO2020244333A1
WO2020244333A1 PCT/CN2020/086681 CN2020086681W WO2020244333A1 WO 2020244333 A1 WO2020244333 A1 WO 2020244333A1 CN 2020086681 W CN2020086681 W CN 2020086681W WO 2020244333 A1 WO2020244333 A1 WO 2020244333A1
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positive electrode
lithium
solid
transition metal
state battery
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PCT/CN2020/086681
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Chinese (zh)
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索鎏敏
李美莹
李泓
陈立泉
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中国科学院物理研究所
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention relates to the field of high-energy density all-solid-state metal lithium batteries, in particular to a novel solid-state battery and its positive electrode material.
  • Lithium-sulfur batteries use the reversible reaction of metallic lithium and elemental sulfur as the energy storage reaction, and their theoretical specific capacity is as high as 1675mAh/g, which is one of the types with the highest energy density among energy storage devices.
  • polysulfide Li 2 S n (2 ⁇ n ⁇ 8) shuttle and metal lithium dendrite formation in traditional liquid lithium-sulfur batteries solid-state lithium-sulfur batteries came into being and are considered to be a complete solution. The ultimate means of lithium-ion battery safety.
  • the present invention is oriented to the application of high-capacity all-solid-state metal lithium-sulfur batteries, and develops a type of positive electrode material with good conductivity and high sulfur loading.
  • Its innovation lies in the choice of a type of transition metal sulfide with ion conductivity and electronic conductivity as the positive electrode material to combine with high-capacity sulfur: this type of sulfide can be used as an electrode material active material to participate in the lithium-sulfur reaction, and it can also play a role The role of the solid electrolyte to provide ion transport channels, thereby greatly reducing the content of electrolyte and conductive additives in the positive electrode material, and providing more space for sulfur loading.
  • transition metal sulfides can replace solid electrolyte 100% for conductivity Additives, so as to achieve a solid electrolyte content of 0 in the positive electrode, thereby greatly improving the volume and mass energy density of this type of positive electrode material.
  • an all-solid-state battery based on transition metal sulfide cathode materials, which greatly reduces the proportion of inactive materials in the cathode materials.
  • the cathode materials are all composed of active materials. Improve the energy density of the cathode material.
  • embodiments of the present invention provide a novel solid-state battery, which includes an embedded lithium-storage positive electrode, a battery electrolyte, and a lithium-rich negative electrode;
  • the positive electrode for embedded lithium storage includes: a positive electrode material containing a transition metal chalcogenide compound for embedded lithium storage and a composite material thereof; the positive electrode material has both ionic conductivity and electronic conductivity, and is formed inside the positive electrode A three-dimensional ion and electronic conductive network structure used for insertion and extraction of lithium ions;
  • the crystal structure of the transition metal chalcogenide compound includes a layered structure or a Scheffler phase, and the transition metal in the transition metal chalcogenide compound includes at least one of group IVB, VB, VIB, and VIIB metal elements; During the insertion and extraction of lithium ions, the transition metal undergoes a valence reaction.
  • the lithium-rich negative electrode is specifically: metallic lithium, lithium alloy, lithium carbon, or silicon-based material containing a current collector, and the silicon-based material is a silicon-based material pre-inserted with lithium.
  • the metal chalcogenide compound is specifically M x S y , and M is a cation, including: one or more of Mo, Ti, V, Cr, Mn, Nb, Zr, W, Re, Ta, and Re ; 1 ⁇ x ⁇ 9, 1 ⁇ y ⁇ 9, and the values of x and y meet the requirements of maintaining the electric neutrality of the compound.
  • the cathode material further includes: S, Li 2 S 8 , Li 2 S 4 , Li 2 S 2 , Li 2 S, mixed with the transition metal chalcogenide compound for embedded lithium storage and its composite material.
  • the positive electrode further includes: 0-30% of the mass of the positive electrode solid electrolyte and 0%-30% of the carbon material.
  • the carbon material includes one or more of Super-P carbon black, carbon fiber, carbon nanotube, graphene, and acetylene black.
  • the mass percentage of the transition metal chalcogenide compound in the composite material is 5%-100%.
  • the battery electrolyte is a solid electrolyte arranged between the positive electrode and the negative electrode, and the battery electrolyte contains a lithium superion conductor material.
  • embodiments of the present invention provide a positive electrode material in the novel solid-state battery according to the first aspect, wherein the positive electrode material includes a transition metal chalcogenide compound with embedded lithium storage and a composite material thereof; the positive electrode material It has both ionic conductivity and electronic conductivity, and a three-dimensional ion and electronic conductive network structure is formed inside the positive electrode, and the network structure is used for lithium ion insertion and extraction;
  • the crystal structure of the transition metal chalcogenide compound includes a layered structure or a Scheffler phase, and the transition metal in the transition metal chalcogenide compound includes at least one of group IVB, VB, VIB, and VIIB metal elements; During the insertion and extraction of lithium ions, the transition metal undergoes a valence reaction.
  • the positive electrode material in the novel solid-state battery provided by the present invention contains a type of transition metal chalcogenide compound.
  • This type of transition metal chalcogenide compound itself has electrochemical activity and can function as an active material. In addition, it has good electronic conductivity. And particle conductivity, can reduce or even eliminate the introduction of solid electrolyte and conductive additives in the positive electrode material, and can completely or partially replace the solid electrolyte and conductive additives in the electrode, thereby effectively increasing the proportion of electrochemically active substances in the electrode, and ultimately increasing
  • the energy density makes the new solid-state battery based on the composite positive electrode have the advantages of high energy density and good safety.
  • the transition metal sulfide of the positive electrode material in the novel solid-state battery of the present invention has good compatibility with sulfur or some traditional positive electrode materials, and when used in conjunction with each other, the mutual electrochemical/chemical stability is good.
  • FIG. 1 is a schematic diagram of the device structure of a novel solid-state battery provided by an embodiment of the present invention
  • Example 2 is a graph showing the charge and discharge curve of the new solid-state battery provided in Example 1 of the present invention when it is cycled to the 20th week;
  • Fig. 3 is a charging and discharging curve diagram of the new solid-state battery provided in Examples 3, 4, 5 and the comparative example when it is cycled to the 20th week, and the specific capacity is calculated by the mass of S in the positive electrode;
  • Example 5 is a graph showing the charge and discharge curves of the new solid-state battery provided in Example 36 of the invention when it is recycled to the 20th week.
  • the embodiment of the present invention provides a novel solid-state battery, including an embedded lithium-storage positive electrode, a battery electrolyte, and a lithium-rich negative electrode;
  • the positive electrode for embedded lithium storage includes: a positive electrode material containing a transition metal chalcogenide compound for embedded lithium storage and a composite material thereof; in the composite material, the mass percentage of the transition metal chalcogenide compound is 5%-100%. That is, the positive electrode of the present invention may be composed of a transition metal chalcogenide alone.
  • the positive electrode material has both ionic conductivity and electronic conductivity, and a three-dimensional ion and electronic conductive network structure is formed inside the positive electrode.
  • the network structure is used for lithium ion insertion and extraction;
  • the crystal structure of the transition metal chalcogenide compound includes a layered structure or Schefferer phase.
  • the transition metal in the transition metal chalcogenide compound includes at least one of the IVB, VB, VIB, VIIB group metal elements; in the lithium ion intercalation and During the extraction process, the transition metal undergoes a valence reaction.
  • the lithium-rich negative electrode is specifically: metallic lithium, lithium alloy, lithium carbon, or silicon-based material containing a current collector
  • the silicon-based material is a silicon-based material pre-inserted with lithium.
  • the silicon-based material is a silicon-based material pre-inserted with lithium, and may include at least one of elemental silicon, silicon alloy, metal-coated silicon, or metal-doped silicon.
  • the positive electrode can also be pre-inserted with lithium.
  • the current collector of the electrode can be selected from one of copper foil, copper mesh, aluminum foil, stainless steel sheet, stainless steel mesh, and nickel foam.
  • the battery electrolyte is a solid electrolyte, which is arranged between the positive electrode and the negative electrode.
  • the battery electrolyte contains a lithium super-ion conductor material. Specifically, it can include: Li 10 GeP 2 S 12 , 75Li 2 S-25P 2 S 5 , 70Li 2 S-30P 2 S 5 , 50Li 2 S-10P 2 S 5 -10LiCl or 50Li 2 S-10P 2 S 5- One of 10Li 3 N, Li 6 PS 5 Cl, Li 10 SnP 2 S 12 , Li 9.54 P 3 S 12 Si 1.74 P 1.44 S 11.7 Cl 0.3 , 75Li 2 S-24P 2 S 5 -P 2 O 5 or Several kinds.
  • the preparation of the solid electrolyte can be a single-layer film structure prepared under external pressure or a composite sheet structure.
  • the film pressing pressure is 2-20 MPa, preferably 8-12 MPa; when using a button cell packaging machine, the film pressure is 40-80 MPa, preferably 50-60 MPa.
  • the structure of the novel solid-state battery is a cylindrical structure or a button structure or a plate structure.
  • the aforementioned metal chalcogenide compound is specifically M x S y , and M is a cation, including: one or more of Mo, Ti, V, Cr, Mn, Nb, Zr, W, Re, Ta, and Re; 1 ⁇ x ⁇ 9, 1 ⁇ y ⁇ 9, and the values of x and y satisfy the need to maintain the compound's electrical neutrality.
  • the positive electrode material also includes: S, Li 2 S 8 , Li 2 S 4 , and Li 2 S 8 , Li 2 S 4 , mixed with transition metal chalcogenides and composite materials for embedded lithium storage.
  • the positive electrode may also include: 0-30% of the mass of the positive electrode solid electrolyte and 0%-30% of the carbon material.
  • the optional components of the solid electrolyte are the same as the battery electrolyte described above.
  • the positive electrode material in the novel solid-state battery provided by the present invention contains a type of transition metal chalcogenide compound.
  • This type of transition metal chalcogenide compound itself has electrochemical activity and can function as an active material. In addition, it has good electronic conductivity. And particle conductivity, can reduce or even eliminate the introduction of solid electrolyte and conductive additives in the positive electrode material, and can completely or partially replace the solid electrolyte and conductive additives in the electrode, thereby effectively increasing the proportion of electrochemically active substances in the electrode, and ultimately increasing
  • the energy density makes the new solid-state battery based on the composite positive electrode have the advantages of high energy density and good safety.
  • the transition metal sulfide of the positive electrode material in the novel solid-state battery of the present invention has good compatibility with sulfur or some traditional positive electrode materials, and when used in conjunction with each other, the mutual electrochemical/chemical stability is good.
  • the transition metal chalcogenide compound and its composite material can reach 70% to 90% of the total mass of the cathode material, and the solid electrolyte addition can be controlled at 0 to 5%.
  • the mixing method of the transition metal chalcogenide compound and its composite material and the other positive electrode materials mentioned above is not limited; for mass production, ball milling can be used.
  • the rotation speed of the ball mill is 100-500rpm, and the time is 1-36 hours. In a further preferred solution, the rotation speed of the ball mill is 300-400 rpm, and the time is 4-12 hours.
  • the novel solid-state battery of the present invention is selected according to different electrolyte materials, and the novel solid-state battery can work at room temperature to 80°C.
  • the typical device structure of the novel solid-state battery described above can be shown in Figure 1, as shown in the figure, including a positive electrode current collector 1, a transition metal chalcogenide compound and its composite material, a positive electrode material 2, a solid battery electrolyte 3, a negative electrode material 4 And the negative current collector 5.
  • the battery includes a positive electrode, a negative electrode and a solid electrolyte (that is, used as a battery electrolyte, the following embodiments are the same).
  • the positive electrode is Mo 6 S 8
  • Li 10 GeP 2 S 12 , 75% Li 2 S-25% P 2 S 5 double-layer solid sulfide electrolyte and lithium sheet are used to assemble an all-solid battery.
  • Li 10 GeP 2 S 12 faces the cathode material
  • 75% Li 2 S-25% P 2 S 5 faces metal lithium.
  • the device structure is shown in Figure 1. 2 is a graph showing the charge and discharge curve of the new solid-state battery provided in Example 1 of the present invention when it is cycled to the 20th week. The specific discharge capacity can reach 97mAh/g in 20-week cycles.
  • This embodiment provides a new high-capacity solid-state battery, which includes a positive electrode, a negative electrode and a solid electrolyte.
  • the positive electrode contains 5% Mo 6 S 8 , 45% S, 20% Li 10 GeP 2 S 12 , 15% graphene, and 15% carbon nanotubes in a mass ratio.
  • the weighed components of the positive electrode material are ball-milled and mixed in an Ar atmosphere for 4 hours to obtain the positive electrode material.
  • the prepared cathode material, Li 10 GeP 2 S 12 , 75% Li 2 S-25% P 2 S 5 double-layer solid sulfide electrolyte and lithium sheet are assembled into an all-solid battery.
  • Li 10 GeP 2 S 12 faces the cathode material
  • 75% Li 2 S-25% P 2 S 5 faces metal lithium.
  • the device structure is shown in Figure 1.
  • This embodiment provides a new high-capacity solid-state battery, which includes a positive electrode, a negative electrode and a solid electrolyte.
  • the positive electrode contains 12.5% Mo 6 S 8 , 37.5% S, 20% Li 10 GeP 2 S 12 , 15% graphene, and 15% carbon nanotubes in a mass ratio.
  • the weighed components of the positive electrode material are ball-milled and mixed in an Ar atmosphere for 4 hours to obtain the positive electrode material.
  • the prepared cathode material, Li 10 GeP 2 S 12 , 75% Li 2 S-25% P 2 S 5 double-layer solid sulfide electrolyte and lithium sheet are assembled into an all-solid battery.
  • Li 10 GeP 2 S 12 faces the cathode material
  • 75% Li 2 S-25% P 2 S 5 faces metal lithium.
  • the device structure is shown in Figure 1.
  • Figure 3 shows the charge and discharge curves of the device at 70°C.
  • the components of the positive electrode material are also calculated by mass ratio.
  • This embodiment provides a new high-capacity solid-state battery, which includes a positive electrode, a negative electrode and a solid electrolyte.
  • the positive electrode contains 25% Mo 6 S 8 , 25% S, 20% Li 10 GeP 2 S 12 , 15% graphene, and 15% carbon nanotubes in a mass ratio.
  • the weighed components of the positive electrode material are ball-milled and mixed in an Ar atmosphere for 4 hours to obtain the positive electrode material.
  • the prepared cathode material, Li 10 GeP 2 S 12 , 75% Li 2 S-25% P 2 S 5 double-layer solid sulfide electrolyte and lithium sheet are assembled into an all-solid battery.
  • Li 10 GeP 2 S 12 faces the cathode material
  • 75% Li 2 S-25% P 2 S 5 faces metal lithium.
  • the device structure is shown in Figure 1.
  • Figure 3 shows the charge and discharge curves of the device at 70°C.
  • This embodiment provides a new high-capacity solid-state battery, which includes a positive electrode, a negative electrode and a solid electrolyte.
  • the positive electrode contains 37.5% Mo 6 S 8 , 12.5% S, 20% Li 10 GeP 2 S 12 , 15% graphene, and 15% carbon nanotubes in a mass ratio.
  • the weighed components of the positive electrode material are ball-milled and mixed in an Ar atmosphere for 4 hours to obtain the positive electrode material.
  • the prepared cathode material, Li 10 GeP 2 S 12 , 75% Li 2 S-25% P 2 S 5 double-layer solid sulfide electrolyte and lithium sheet are assembled into an all-solid battery.
  • Li 10 GeP 2 S 12 faces the cathode material
  • 75% Li 2 S-25% P 2 S 5 faces metal lithium.
  • the device structure is shown in Figure 1.
  • Figure 3 shows the charge and discharge curves of the device at 70°C.
  • This embodiment provides a new high-capacity solid-state battery, which includes a positive electrode, a negative electrode and a solid electrolyte.
  • the positive electrode contains 45% Mo 6 S 8 , 15% S, 20% Li 10 GeP 2 S 12 , 10% graphene, and 10% carbon nanotubes in a mass ratio.
  • the weighed components of the positive electrode material are ball-milled and mixed in an Ar atmosphere for 4 hours to obtain the positive electrode material.
  • the prepared cathode material, Li 10 GeP 2 S 12 , 75% Li 2 S-25% P 2 S 5 double-layer solid sulfide electrolyte and lithium sheet are assembled into an all-solid battery.
  • Li 10 GeP 2 S 12 faces the cathode material
  • 75% Li 2 S-25% P 2 S 5 faces metal lithium.
  • the device structure is shown in Figure 1.
  • This embodiment provides a new high-capacity solid-state battery, which includes a positive electrode, a negative electrode and a solid electrolyte.
  • the positive electrode contains 45% TiS 2 , 15% S, 20% Li 10 GeP 2 S 12 , 10% graphene, and 10% carbon nanotubes in a mass ratio.
  • the weighed components of the positive electrode material are mixed by ball milling under an Ar atmosphere, and the ball milling time is 4 hours to obtain the positive electrode material.
  • the prepared cathode material, Li 10 GeP 2 S 12 , 75% Li 2 S-25% P 2 S 5 double-layer solid sulfide electrolyte and lithium sheet are assembled into an all-solid battery.
  • Li 10 GeP 2 S 12 faces the cathode material
  • 75% Li 2 S-25% P 2 S 5 faces metal lithium.
  • the device structure is shown in Figure 1.
  • This embodiment provides a new high-capacity solid-state battery, which includes a positive electrode, a negative electrode and a solid electrolyte.
  • the positive electrode contains 60% Mo 6 S 8 , 20% S, 10% graphene, and 10% carbon nanotubes in a mass ratio.
  • the weighed components of the positive electrode material are ball-milled and mixed in an Ar atmosphere for 4 hours to obtain the positive electrode material.
  • the prepared cathode material, Li 10 GeP 2 S 12 , 75% Li 2 S-25% P 2 S 5 double-layer solid sulfide electrolyte and lithium sheet are assembled into an all-solid battery.
  • Li 10 GeP 2 S 12 faces the cathode material
  • 75% Li 2 S-25% P 2 S 5 faces metal lithium.
  • the device structure is shown in Figure 1. 4 is a graph showing the charge and discharge curves of the new solid-state battery provided by Invention Example 8 and the solid-state battery in the comparative example when it is cycled to the 20th week.
  • the specific discharge capacity of the 20-week cycle is much higher than that of the material provided in the comparative example.
  • This embodiment provides a new high-capacity solid-state battery, which includes a positive electrode, a negative electrode and a solid electrolyte.
  • the positive electrode contains 95% Mo 6 S 8 , 4% S, 0.5% graphene, and 0.5% carbon nanotubes in a mass ratio.
  • the weighed components of the positive electrode material are ball-milled and mixed in an Ar atmosphere for 4 hours to obtain the positive electrode material.
  • the prepared cathode material, Li 10 GeP 2 S 12 , 75% Li 2 S-25% P 2 S 5 double-layer solid sulfide electrolyte and lithium sheet are assembled into an all-solid battery.
  • Li 10 GeP 2 S 12 faces the cathode material
  • 75% Li 2 S-25% P 2 S 5 faces metal lithium.
  • the device structure is shown in Figure 1.
  • This embodiment provides a new high-capacity solid-state battery, which includes a positive electrode, a negative electrode and a solid electrolyte.
  • the positive electrode contains 82% Mo 6 S 8 , 13% S, 2.5% graphene, and 2.5% carbon nanotubes in a mass ratio.
  • the weighed components of the positive electrode material are ball-milled and mixed in an Ar atmosphere for 4 hours to obtain the positive electrode material.
  • the prepared cathode material, Li 10 GeP 2 S 12 , 75% Li 2 S-25% P 2 S 5 double-layer solid sulfide electrolyte and lithium sheet are assembled into an all-solid battery.
  • Li 10 GeP 2 S 12 faces the cathode material
  • 75% Li 2 S-25% P 2 S 5 faces metal lithium.
  • the device structure is shown in Figure 1.
  • This embodiment provides a new high-capacity solid-state battery, which includes a positive electrode, a negative electrode and a solid electrolyte.
  • the positive electrode contains 70% Mo 6 S 8 and 30% S by mass ratio.
  • the weighed components of the positive electrode material are ball-milled and mixed in an Ar atmosphere for 4 hours to obtain the positive electrode material.
  • the prepared cathode material, Li 10 GeP 2 S 12 , 75% Li 2 S-25% P 2 S 5 double-layer solid sulfide electrolyte and lithium sheet are assembled into an all-solid battery.
  • Li 10 GeP 2 S 12 faces the cathode material
  • 75% Li 2 S-25% P 2 S 5 faces metal lithium.
  • the device structure is shown in Figure 1.
  • This embodiment provides a new high-capacity solid-state battery, which includes a positive electrode, a negative electrode and a solid electrolyte.
  • the positive electrode contains 5% Mo 6 S 8 and 95% S by mass ratio.
  • the weighed components of the positive electrode material are ball-milled and mixed in an Ar atmosphere for 4 hours to obtain the positive electrode material.
  • the prepared cathode material, Li 10 GeP 2 S 12 , 75% Li 2 S-25% P 2 S 5 double-layer solid sulfide electrolyte and lithium sheet are assembled into an all-solid battery.
  • Li 10 GeP 2 S 12 faces the cathode material
  • 75% Li 2 S-25% P 2 S 5 faces metal lithium.
  • the device structure is shown in Figure 1.
  • This embodiment provides a new high-capacity solid-state battery, which includes a positive electrode, a negative electrode and a solid electrolyte.
  • the positive electrode contains 63% Mo 6 S 8 , 27% S, 5% Li 10 GeP 2 S 12 , 2.5% graphene, and 2.5% carbon nanotubes in mass ratio.
  • the weighed components of the positive electrode material are ball-milled and mixed in an Ar atmosphere for 4 hours to obtain the positive electrode material.
  • the prepared cathode material, Li 10 GeP 2 S 12 , 75% Li 2 S-25% P 2 S 5 double-layer solid sulfide electrolyte and lithium sheet are assembled into an all-solid battery.
  • Li 10 GeP 2 S 12 faces the cathode material
  • 75% Li 2 S-25% P 2 S 5 faces metal lithium.
  • the device structure is shown in Figure 1.
  • This embodiment provides a new high-capacity solid-state battery, which includes a positive electrode, a negative electrode and a solid electrolyte.
  • the positive electrode contains 56% Mo 6 S 8 , 24% S, 5% Li 10 GeP 2 S 12 , 7.5% graphene, and 7.5% carbon nanotubes in a mass ratio.
  • the weighed components of the positive electrode material are ball-milled and mixed in an Ar atmosphere for 4 hours to obtain the positive electrode material.
  • the prepared cathode material, Li 10 GeP 2 S 12 , 75% Li 2 S-25% P 2 S 5 double-layer solid sulfide electrolyte and lithium sheet are assembled into an all-solid battery.
  • Li 10 GeP 2 S 12 faces the cathode material
  • 75% Li 2 S-25% P 2 S 5 faces metal lithium.
  • the device structure is shown in Figure 1.
  • Example 15 to Example 28 are the same as those in Example 14, except that the transition metal sulfide mixture in the positive electrode material is different. See Table 1 for details.
  • This embodiment provides a new high-capacity solid-state battery, which includes a positive electrode, a negative electrode and a solid electrolyte.
  • the positive electrode contains 70% Mo 6 S 8 and 30% LiFePO 4 in a mass ratio.
  • the weighed components of the positive electrode material are ball-milled and mixed in an Ar atmosphere for 4 hours to obtain the positive electrode material.
  • the prepared cathode material, Li 10 GeP 2 S 12 , 75% Li 2 S-25% P 2 S 5 double-layer solid sulfide electrolyte and lithium sheet are assembled into an all-solid battery.
  • Li 10 GeP 2 S 12 faces the cathode material
  • 75% Li 2 S-25% P 2 S 5 faces metal lithium.
  • the device structure is shown in Figure 1.
  • Example 30 to Example 36 are the same as those in Example 29, except that the mixed types of other positive electrode materials in the positive electrode material and the proportion of each component are different. See Table 1 for details.
  • Fig. 5 is a charging and discharging curve diagram of the new solid-state battery provided by Invention Example 36 when it is recycled to the 20th week, and the specific capacity can reach 159 mAh/g based on the total mass of the positive electrode.
  • the battery includes a positive electrode, a negative electrode and a solid electrolyte.
  • the positive electrode contains 20% elemental sulfur, 40% graphene, and 40% carbon nanotubes in a mass ratio.
  • the weighed components of the positive electrode material are mixed by ball milling under an inert atmosphere for 4 hours to obtain the positive electrode material.
  • the prepared positive electrode material, Li 10 GeP 2 S 12 , and 75% Li 2 S-25% P 2 S 5 double-layer solid sulfide electrolyte and lithium sheets are assembled into an all-solid lithium-sulfur battery.
  • Li 10 GeP 2 S 12 faces the cathode material
  • 75% Li 2 S-25% P 2 S 5 faces metal lithium.
  • the device structure is the same as shown in Figure 1.
  • Figure 4 shows the charge and discharge curves of the device at 70°C.
  • the mass is based on the active material, and the discharge specific capacity is only 16 mAh/g in 20 weeks, and the mass is based on the total mass of the positive electrode, and the discharge specific capacity in 20 cycles is only 3.2 mAh/g.
  • the charging and discharging current of all the above examples is 15uA, and they are all tested at 70°C.
  • the active material is based on the mass of metal sulfide; when the positive electrode contains S or Li 2 S x , the active material is based on the mass of S or Li 2 S x ; the positive electrode contains metal sulfide and lithium-containing positive electrode When the material is used, the active material is calculated based on the total mass of metal sulfide and lithium-containing cathode material.
  • the positive electrode material in the novel solid-state battery provided by the present invention contains a type of transition metal chalcogenide compound.
  • This type of transition metal chalcogenide compound itself has electrochemical activity and can function as an active material. In addition, it has good electronic conductivity. And particle conductivity, can reduce or even eliminate the introduction of solid electrolyte and conductive additives in the positive electrode material, and can completely or partially replace the solid electrolyte and conductive additives in the electrode, thereby effectively increasing the proportion of electrochemically active substances in the electrode, and ultimately increasing
  • the energy density makes the new solid-state battery based on the composite positive electrode have the advantages of high energy density and good safety.
  • the transition metal sulfide of the positive electrode material in the novel solid-state battery of the present invention has good compatibility with sulfur or some traditional positive electrode materials, and when used in conjunction with each other, the electrochemical/chemical stability is good.
  • the specific embodiments described above further describe the purpose, technical solutions and beneficial effects of the present invention in further detail. It should be understood that the above are only specific embodiments of the present invention and are not intended to limit the scope of the present invention. The scope of protection, any modification, equivalent replacement, improvement, etc., made within the spirit and principle of the present invention shall be included in the scope of protection of the present invention.

Abstract

L'invention concerne une nouvelle batterie à semi-conducteur et un matériau d'électrode positive (2) associé. La batterie à semi-conducteur comprend une électrode positive de stockage de lithium incorporée, un électrolyte de batterie (3) et une électrode négative riche en lithium. L'électrode positive de stockage de lithium incorporée comprend : le matériau d'électrode positive (2) comprenant un chalcogénure de métal de transition stockant du lithium intégré et un matériau composite de celui-ci. Le matériau d'électrode positive (2) fournit simultanément une conductivité ionique et une conductivité électronique et constitue une structure de réseau électroconductrice et électronique tridimensionnelle à l'intérieur de l'électrode positive, la structure de réseau étant utilisée pour l'incorporation et l'évacuation d'ions lithium. Une structure cristalline du chalcogénure de métal de transition comprend une structure lamellaire ou une phase de Chevrell. Les métaux de transition du chalcogénure de métal de transition comprennent au moins un des éléments métalliques du groupe IVB, VB, VIB et VIIB. Dans un procédé d'incorporation et d'évacuation d'ions lithium, les métaux de transition subissent une réaction de valence. L'introduction du matériau d'électrode positive (2) remplace entièrement ou partiellement un électrolyte et un additif électroconducteur dans un matériau d'électrode positive classique, réduit efficacement le pourcentage en poids d'une substance inactive dans une batterie, et augmente la densité d'énergie de l'électrolyte à semi-conducteur (3).
PCT/CN2020/086681 2019-06-04 2020-04-24 Nouvelle batterie à semi-conducteur et matériau d'électrode positive associé WO2020244333A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105027346A (zh) * 2013-03-26 2015-11-04 古河电气工业株式会社 全固态二次电池
CN106898750A (zh) * 2017-03-28 2017-06-27 苏州大学 基于富硫过渡金属硫化物的金属‑硫电池及其制备方法
CN108232164A (zh) * 2018-01-15 2018-06-29 中南大学 一种锂硫电池正极材料及其制备方法
CN108352510A (zh) * 2015-11-09 2018-07-31 罗伯特·博世有限公司 全固态再充式锂电池

Family Cites Families (3)

* Cited by examiner, † Cited by third party
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JP3995050B2 (ja) * 2003-09-26 2007-10-24 Ｊｆｅケミカル株式会社 リチウムイオン二次電池負極材料用複合粒子およびその製造方法、リチウムイオン二次電池用負極材料および負極、ならびにリチウムイオン二次電池
JP5571281B2 (ja) * 2007-11-16 2014-08-13 パナソニック株式会社 全固体型ポリマー電池およびその製造方法
WO2015105140A1 (fr) * 2014-01-08 2015-07-16 国立大学法人京都大学 Batterie secondaire

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105027346A (zh) * 2013-03-26 2015-11-04 古河电气工业株式会社 全固态二次电池
CN108352510A (zh) * 2015-11-09 2018-07-31 罗伯特·博世有限公司 全固态再充式锂电池
CN106898750A (zh) * 2017-03-28 2017-06-27 苏州大学 基于富硫过渡金属硫化物的金属‑硫电池及其制备方法
CN108232164A (zh) * 2018-01-15 2018-06-29 中南大学 一种锂硫电池正极材料及其制备方法

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