WO2020244333A1 - Novel solid-state battery and positive electrode material thereof - Google Patents

Novel solid-state battery and positive electrode material thereof Download PDF

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Publication number
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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French (fr)
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

A novel solid-state battery and a positive electrode material (2) thereof. The solid-state battery comprises an embedded lithium-storing positive electrode, a battery electrolyte (3), and a lithium-rich negative electrode. The embedded lithium-storing positive electrode comprises: the positive electrode material (2) comprising an embedded lithium-storing transitional metal chalcogenide and a composite material thereof. The positive electrode material (2) simultaneously provides ionic conductivity and electronic conductivity and constitutes a three-dimensional ionic and electronic electrically-conductive network structure within the positive electrode, the network structure being used for lithium ion embedment and escape. A crystal structure of the transitional metal chalcogenide comprises a lamellar structure or a Chevrell phase. Transitional metals of the transitional metal chalcogenide comprise at least one of group IVB, VB, VIB, and VIIB metal elements. In a lithium-ion embedment and escape process, the transitional metals undergo a valance reaction. The introduction of the positive electrode material (2) entirely or partly replaces an electrolyte and an electrically-conductive additive in a conventional positive electrode material, effectively reduces the weight percentage of an inactive substance in a battery, and increases the energy density of the solid-state electrolyte (3).

Description

新型固态电池及其正极材料New solid state battery and its cathode material
本申请要求于2019年06月04日提交中国专利局、申请号为201910481599.8、发明名称为“新型固态电池及其正极材料”的中国专利申请的优先权。This application claims the priority of a Chinese patent application filed with the Chinese Patent Office with the application number 201910481599.8 and the invention title of "New Solid State Batteries and Cathode Materials" on June 4, 2019.
技术领域Technical field
本发明涉及高能量密度全固态金属锂电池领域，尤其涉及一种新型固态电池及其正极材料。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.
背景技术Background technique
储能技术水平关乎军事国防、交通输运、便携电子等多个领域的发展，更高的能量密度、更安全的工作状态、更稳定的输运性能是储能器件的发展方向。锂硫电池采用金属锂和单质硫的可逆反应作为储能反应，其理论比容量高达1675mAh/g，是目前储能器件中能量密度最高的种类之一。为了解决传统液态锂硫电池中多硫化物Li 2S n(2<n<8)穿梭、金属锂枝晶生成等对电池造成的不利影响，固态锂硫电池应运而生，被认为是彻底解决锂离子电池安全性的终极手段。 The level of energy storage technology is related to the development of military and defense, transportation, portable electronics and other fields. Higher energy density, safer working conditions, and more stable transport performance are the development directions of energy storage devices. 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. In order to solve the adverse effects on the battery caused by 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.
然而，对于固态锂硫电池来说，硫单质的电子导电性和离子导电性都很低，而固态电解质对正极材料的浸润作用又极弱，这将限制正极材料中硫离子的输运，进而限制电池的容量。为了增加正极材料的导电性，人们减小硫单质的颗粒，增加其在正极材料中的分散性，同时在正极中参入大量的电解质和导电碳。然而，这些物质的引入会大大降低正极材料中单质硫的负载量，影响实际电池容量。为了将锂硫电池的容量优势发挥出来，一个导电性高、能量密度高的正极材料是目前全固态锂硫电池走向应用的必然要求。However, for solid-state lithium-sulfur batteries, the electronic conductivity and ionic conductivity of the elemental sulfur are very low, and the solid electrolyte has very weak infiltration effect on the cathode material, which will limit the transport of sulfur ions in the cathode material, and thus Limit the capacity of the battery. In order to increase the conductivity of the positive electrode material, people reduce the elemental sulfur particles and increase its dispersibility in the positive electrode material. At the same time, a large amount of electrolyte and conductive carbon are incorporated in the positive electrode. However, the introduction of these substances will greatly reduce the loading of elemental sulfur in the positive electrode material and affect the actual battery capacity. In order to give full play to the capacity advantages of lithium-sulfur batteries, a cathode material with high conductivity and high energy density is an inevitable requirement for the application of all-solid-state lithium-sulfur batteries.
本发明面向高容量全固态金属锂硫电池的应用，开发出一类导电性好、硫负载量高的正极材料。其创新之处在于，选择一类具有离子导电性和电子导电性的过渡金属硫化物作为正极材料与高容量硫复合：该类硫化物既可以作为电极材料活性物质参与锂硫反应，又可以起到固体电解质的作用提供离子传输通道，从而大幅减少正极材料中的电解质和导电添加剂的含量，为硫的负载提供更大的空间，在极限条件下，过渡金属硫化物可以100％替代固体电解质导电添加剂，从而实现正极中固体电解质含量为0，进而大大提高了该类正极材料的体积和质量能量密度。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. Under extreme conditions, 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.
发明内容Summary of the invention
为了提升全固态电池的能量密度，我们提出一种基于过渡金属硫化物正极材料的全固态电池，使得正极材料中非活性物质的占比大大下降，极端情况下正极材料全部由活性物质构成，从而提高正极材料的能量密度。In order to improve the energy density of all-solid-state batteries, we propose an all-solid-state battery based on transition metal sulfide cathode materials, which greatly reduces the proportion of inactive materials in the cathode materials. In extreme cases, the cathode materials are all composed of active materials. Improve the energy density of the cathode material.
为实现上述目的，第一方面，本发明实施例提供了一种新型固态电池，所述新型固态电池包括嵌入式储锂的正极、电池电解质以及富锂负极；To achieve the foregoing objective, in the first aspect, 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;
所述嵌入式储锂的正极包括：包含嵌入式储锂的过渡金属硫族化合物及其复合材料的正极材料；所述正极材料同时具备离子导电性和电子导电性，并且在所述正极内部构成三维离子、电子导电网络结构，所述网络结构用以锂离子嵌入和脱出；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;
所述过渡金属硫族化合物的晶体结构包括层状结构或谢弗雷尔相，所述过渡金属硫族化合物中的过渡金属包括IVB，VB，VIB，VIIB族金属元素中的至少一种；在所述锂离子嵌入和脱出过程中，所述过渡金属发生变价反应。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.
优选的，所述富锂负极具体为：包含集流体的金属锂、锂合金、锂碳或硅基材料，所述硅基材料为预嵌锂的硅基材料。Preferably, 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.
优选的，所述金属硫族化合物具体为M xS y，M为阳离子，包括：Mo,Ti, V,Cr,Mn,Nb,Zr,W,Re,Ta，Re中的一种或多种；1≤x≤9，1≤y≤9，且x、y的取值满足保持化合物电中性。 Preferably, 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.
优选的，所述正极材料还包括：与所述嵌入式储锂的过渡金属硫族化合物及其复合材料混合的S,Li 2S 8,Li 2S 4,Li 2S 2,Li 2S,LiFePO 4,LiMn 2O 4,LiCoO 2,LiNi 0.5Mn 1.5O 4,LiNi 0.5Mn 0.5O 2,LiNiO 2,LiNi 1/3Co 1/3Mn 1/3O 2,LiNi 0.5Co 0.3Mn 0.2O 2,LiNi 0.6Co 0.2Mn 0.2O 2,LiNi 0.8Co 0.1Mn 0.1O 2,LiNiCoAlO 2,Li 4Ti 5O 12中的一种或多种正极材料。 Preferably, 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. LiFePO 4 ,LiMn 2 O 4 ,LiCoO 2 ,LiNi 0.5 Mn 1.5 O 4 ,LiNi 0.5 Mn 0.5 O 2 ,LiNiO 2 ,LiNi 1/3 Co 1/3 Mn 1/3 O 2 ,LiNi 0.5 Co 0.3 Mn 0.2 O 2, LiNi 0.6 Co 0.2 Mn 0.2 O 2, LiNi 0.8 Co 0.1 Mn 0.1 O 2, LiNiCoAlO 2 , Li 4 Ti 5 O 12 and one or more cathode materials.
优选的，所述正极还包括：占正极质量0～30％的固态电解质和0％～30％的碳材料。Preferably, the positive electrode further includes: 0-30% of the mass of the positive electrode solid electrolyte and 0%-30% of the carbon material.
进一步优选的，所述碳材料包括Super-P炭黑、碳纤维、碳纳米管、石墨烯、乙炔黑中的一种或多种。Further preferably, the carbon material includes one or more of Super-P carbon black, carbon fiber, carbon nanotube, graphene, and acetylene black.
优选的，所述复合材料中，过渡金属硫族化合物所占的质量百分比为5％～100％。Preferably, the mass percentage of the transition metal chalcogenide compound in the composite material is 5%-100%.
优选的，所述电池电解质为固态的电解质，设置于正极和负极之间，所述电池电解质含有锂超离子导体材料。Preferably, 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.
第二方面，本发明实施例提供了一种第一方面所述的新型固态电池中的正极材料，所述正极材料包括嵌入式储锂的过渡金属硫族化合物及其复合材料；所述正极材料同时具备离子导电性和电子导电性，并且在所述正极内部构成三维离子、电子导电网络结构，所述网络结构用以锂离子嵌入和脱出；In a second aspect, 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;
所述过渡金属硫族化合物的晶体结构包括层状结构或谢弗雷尔相，所述过渡金属硫族化合物中的过渡金属包括IVB，VB，VIB，VIIB族金属元素中的至少一种；在所述锂离子嵌入和脱出过程中，所述过渡金属发生变价反应。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.
本发明提供的新型固态电池中的正极材料含有一类过渡金属硫族化合物，这类过渡金属硫族化合物本身具有电化学活性，可以起到活性物质的作 用，此外其具有较好的电子导电性和粒子导电性，可以降低甚至免除正极材料中固态电解质和导电添加剂的引入，可以全部或部分取代电极中的固态电解质和和导电添加剂，从而有效提高电极中电化学活性物质的占比，最终提高能量密度，使得基于该复合正极的新型固态电池具有能量密度高、安全性好等优点。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.
本发明新型固态电池中正极材料的过渡金属硫化物与硫或一些传统正极材料具有很好地兼容性，相互配合使用时，相互之间电化学/化学稳定性好。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.
附图说明Description of the drawings
图1为本发明实施例提供的新型固态电池的器件结构示意图；FIG. 1 is a schematic diagram of the device structure of a novel solid-state battery provided by an embodiment of the present invention;
图2为本发明实施例1提供的新型固态电池在循环至第20周时的充放电曲线图；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;
图3为本发明实施例3、4、5和对比例提供的新型固态电池在循环至第20周时的充放电曲线图，比容量按正极中的S质量计；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;
图4为发明实施例8提供的新型固态电池和对比例中的固态电池在循环至第20周时的充放电曲线图；4 is a graph showing 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;
图5为发明实施例36提供的新型固态电池再循环至第20周时的充放电曲线图。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.
具体实施方式Detailed ways
本发明实施例提供了一种新型固态电池，包括嵌入式储锂的正极、电池电解质以及富锂负极；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;
嵌入式储锂的正极包括：包含嵌入式储锂的过渡金属硫族化合物及其复合材料的正极材料；复合材料中，过渡金属硫族化合物所占的质量百分比为5％～100％。也就是说，本发明的正极，可以单独由过渡金属硫族化合物构成。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.
正极材料同时具备离子导电性和电子导电性，并且在正极内部构成三维离子、电子导电网络结构，网络结构用以锂离子嵌入和脱出；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;
过渡金属硫族化合物的晶体结构包括层状结构或谢弗雷尔相，过渡金属硫族化合物中的过渡金属包括IVB，VB，VIB，VIIB族金属元素中的至少一种；在锂离子嵌入和脱出过程中，过渡金属发生变价反应。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.
其中，富锂负极具体为：包含集流体的金属锂、锂合金、锂碳或硅基材料，所述硅基材料为预嵌锂的硅基材料。具体的，硅基材料为预嵌锂的硅基材料，可以包括单质硅、硅合金、金属包覆的硅或金属掺杂的硅中的至少一种。此外，在电极材料不含锂时，还可以对正极也进行预嵌锂处理。电极的集流体可以选自铜箔、铜网、铝箔、不锈钢片、不锈钢网、泡沫镍中的一种。Wherein, 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. Specifically, 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. In addition, when the electrode material does not contain lithium, 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.
电池电解质为固态的电解质，设置于正极和负极之间，电池电解质含有锂超离子导体材料。具体可以包括括：Li 10GeP 2S 12、75Li 2S-25P 2S 5、70Li 2S-30P 2S 5、50Li 2S-10P 2S 5-10LiCl或50Li 2S-10P 2S 5-10Li 3N、Li 6PS 5Cl、Li 10SnP 2S 12、Li 9.54P 3S 12Si 1.74P 1.44S 11.7Cl 0.3、75Li 2S-24P 2S 5-P 2O 5中的一种或几种。 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.
固态电解质的制备可以是经外界压力制备得到的单层薄膜结构或者为复合片层结构。当采用压机给压时，薄膜压制压力为2～20MPa，优选压力为8～12MPa；当采用扣式电池封装机给压时，薄膜压力为40～80MPa，优选为50～60MPa。优选的，新型固态电池的构造为圆筒形结构或扣式结构或板式结构。The preparation of the solid electrolyte can be a single-layer film structure prepared under external pressure or a composite sheet structure. When using a press, 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. Preferably, the structure of the novel solid-state battery is a cylindrical structure or a button structure or a plate structure.
上述金属硫族化合物具体为M xS y，M为阳离子，包括：Mo,Ti,V,Cr,Mn,Nb,Zr,W,Re,Ta，Re中的一种或多种；1≤x≤9，1≤y≤9，且x、y的取值满足保持化合物电中性。 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.
除上述所述的金属硫族化合物及其复合材料之外，正极材料还包括：与嵌入式储锂的过渡金属硫族化合物及其复合材料混合的S,Li 2S 8,Li 2S 4,Li 2S 2,Li 2S,LiFePO 4,LiMn 2O 4,LiCoO 2,LiNi 0.5Mn 1.5O 4,LiNi 0.5Mn 0.5O 2,LiNiO 2, LiNi 1/3Co 1/3Mn 1/3O 2,LiNi 0.5Co 0.3Mn 0.2O 2,LiNi 0.6Co 0.2Mn 0.2O 2,LiNi 0.8Co 0.1Mn 0.1O 2,LiNiCoAlO 2,Li 4Ti 5O 12中的一种或多种正极材料。 In addition to the above-mentioned metal chalcogenide compounds and their composite materials, 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. Li 2 S 2 , Li 2 S, LiFePO 4 , LiMn 2 O 4 , LiCoO 2 , LiNi 0.5 Mn 1.5 O 4 , LiNi 0.5 Mn 0.5 O 2 , LiNiO 2 , LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiNi 0.5 Co 0.3 Mn 0.2 O 2, LiNi 0.6 Co 0.2 Mn 0.2 O 2, LiNi 0.8 Co 0.1 Mn 0.1 O 2, LiNiCoAlO 2 , Li 4 Ti 5 O 12 , one or more of the cathode materials.
此外，正极还可以包括：占正极质量0～30％的固态电解质和0％～30％的碳材料。固态电解质可选成分与上述电池电解质相同。In addition, 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.
本发明提供的新型固态电池中的正极材料含有一类过渡金属硫族化合物，这类过渡金属硫族化合物本身具有电化学活性，可以起到活性物质的作用，此外其具有较好的电子导电性和粒子导电性，可以降低甚至免除正极材料中固态电解质和导电添加剂的引入，可以全部或部分取代电极中的固态电解质和和导电添加剂，从而有效提高电极中电化学活性物质的占比，最终提高能量密度，使得基于该复合正极的新型固态电池具有能量密度高、安全性好等优点。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.
本发明新型固态电池中正极材料的过渡金属硫化物与硫或一些传统正极材料具有很好地兼容性，相互配合使用时，相互之间电化学/化学稳定性好。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.
在较为优选的方案中，为了达到较高的能量密度，过渡金属硫族化合物及其复合材料可以达到正极材料总质量的70％～90％，固态电解质添加量可以控制在0～5％。其中，过渡金属硫族化合物及其复合材料与上述所提及的其它正极材料的混合方式不限；应对大批量生产，可以采用球磨的方式。球磨转速为100～500rpm,时间为1～36小时。在进一步优选的方案中，球磨转速为300～400rpm,时间为4～12小时。In a more preferred solution, in order to achieve a higher energy density, 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%. Among them, 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.
本发明新型固态电池根据电解质材料选择的不同，该新型固态电池可以在室温至80℃下工作。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.
上述描述的新型固态电池的典型器件结构可以如图1所示，如图示包括正极集流体1、过渡金属硫族化合物及其复合材料构成的正极材料2、固态的电池电解质3、负极材料4和负极集流体5。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.
下面结合具体实施例对本发明进行进一步说明。The present invention will be further described below in conjunction with specific embodiments.
实施例1Example 1
本实施例提供了一种高容量的新型固态电池，电池包括正极，负极和固态电解质(即用作电池电解质，以下各实施例相同)。This embodiment provides a new high-capacity solid-state battery. 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).
正极为Mo 6S 8，利用Li 10GeP 2S 12、75％Li 2S-25％P 2S 5双层固态硫化物电解质以及锂片组装成全固态电池。其中Li 10GeP 2S 12朝向正极材料，75％Li 2S-25％P 2S 5朝向金属锂。器件结构如图1所示。图2为本发明实施例1提供的新型固态电池在循环至第20周时的充放电曲线图。20周循环的放电比容量可达97mAh/g。 The positive electrode is Mo 6 S 8 , and 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. Among them, Li 10 GeP 2 S 12 faces the cathode material, and 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.
实施例2Example 2
本实施例提供了一种高容量的新型固态电池，电池包括正极，负极和固态电解质。This embodiment provides a new high-capacity solid-state battery, which includes a positive electrode, a negative electrode and a solid electrolyte.
正极按质量比包含5％的Mo 6S 8、45％的S、20％的Li 10GeP 2S 12、15％的石墨烯，15％的碳纳米管。将称好的正极材料各组分在Ar气氛下球磨混合，球磨时间为4小时，得到正极材料。 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.
将所制备的正极材料、Li 10GeP 2S 12、75％Li 2S-25％P 2S 5双层固态硫化物电解质以及锂片组装成全固态电池。其中Li 10GeP 2S 12朝向正极材料，75％Li 2S-25％P 2S 5朝向金属锂。器件结构如图1所示。 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. Among them, Li 10 GeP 2 S 12 faces the cathode material, and 75% Li 2 S-25% P 2 S 5 faces metal lithium. The device structure is shown in Figure 1.
实施例3Example 3
本实施例提供了一种高容量的新型固态电池，电池包括正极，负极和固态电解质。正极按质量比包含12.5％的Mo 6S 8、37.5％的S、20％的Li 10GeP 2S 12、15％的石墨烯，15％的碳纳米管。将称好的正极材料各组分在Ar气氛下球磨混合，球磨时间为4小时，得到正极材料。 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.
将所制备的正极材料、Li 10GeP 2S 12、75％Li 2S-25％P 2S 5双层固态硫化物电解质以及锂片组装成全固态电池。其中Li 10GeP 2S 12朝向正极材料，75％Li 2S-25％P 2S 5朝向金属锂。器件结构如图1所示。 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. Among them, Li 10 GeP 2 S 12 faces the cathode material, and 75% Li 2 S-25% P 2 S 5 faces metal lithium. The device structure is shown in Figure 1.
图3为该器件在70℃下的充放电曲线。Figure 3 shows the charge and discharge curves of the device at 70°C.
Mo 6S 8/S在1：3的情况下，20周循环的放电比容量可达202mAh/g。 When Mo 6 S 8 /S is 1:3, the specific discharge capacity can reach 202 mAh/g after 20 cycles.
以下各实施例，正极材料各组分也均是以质量比计。In the following embodiments, the components of the positive electrode material are also calculated by mass ratio.
实施例4Example 4
本实施例提供了一种高容量的新型固态电池，电池包括正极，负极和固态电解质。正极按质量比包含25％的Mo 6S 8、25％的S、20％的Li 10GeP 2S 12、15％的石墨烯，15％的碳纳米管。将称好的正极材料各组分在Ar气氛下球磨混合，球磨时间为4小时，得到正极材料。 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.
将所制备的正极材料、Li 10GeP 2S 12、75％Li 2S-25％P 2S 5双层固态硫化物电解质以及锂片组装成全固态电池。其中Li 10GeP 2S 12朝向正极材料，75％Li 2S-25％P 2S 5朝向金属锂。器件结构如图1所示。 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. Among them, Li 10 GeP 2 S 12 faces the cathode material, and 75% Li 2 S-25% P 2 S 5 faces metal lithium. The device structure is shown in Figure 1.
图3为该器件在70℃下的充放电曲线。Figure 3 shows the charge and discharge curves of the device at 70°C.
Mo 6S 8/S在1：1的情况下，20周循环的放电比容量可达309mAh/g。 When Mo 6 S 8 /S is 1:1, the specific discharge capacity can reach 309mAh/g in 20 cycles.
实施例5Example 5
本实施例提供了一种高容量的新型固态电池，电池包括正极，负极和固态电解质。正极按质量比包含37.5％的Mo 6S 8、12.5％的S、20％的Li 10GeP 2S 12、15％的石墨烯，15％的碳纳米管。将称好的正极材料各组分在Ar气氛下球磨混合，球磨时间为4小时，得到正极材料。 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.
将所制备的正极材料、Li 10GeP 2S 12、75％Li 2S-25％P 2S 5双层固态硫化物电解质以及锂片组装成全固态电池。其中Li 10GeP 2S 12朝向正极材料，75％Li 2S-25％P 2S 5朝向金属锂。器件结构如图1所示。 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. Among them, Li 10 GeP 2 S 12 faces the cathode material, and 75% Li 2 S-25% P 2 S 5 faces metal lithium. The device structure is shown in Figure 1.
图3为该器件在70℃下的充放电曲线。Figure 3 shows the charge and discharge curves of the device at 70°C.
Mo 6S 8/S在3：1的情况下，20周循环的放电比容量可达980mAh/g。 When Mo 6 S 8 /S is 3:1, the specific discharge capacity can reach 980mAh/g after 20 cycles.
实施例6Example 6
本实施例提供了一种高容量的新型固态电池，电池包括正极，负极和固态电解质。正极按质量比包含45％的Mo 6S 8、15％的S、20％的Li 10GeP 2S 12、10％的石墨烯，10％的碳纳米管。将称好的正极材料各组分在Ar气氛下球磨混合， 球磨时间为4小时，得到正极材料。 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.
将所制备的正极材料、Li 10GeP 2S 12、75％Li 2S-25％P 2S 5双层固态硫化物电解质以及锂片组装成全固态电池。其中Li 10GeP 2S 12朝向正极材料，75％Li 2S-25％P 2S 5朝向金属锂。器件结构如图1所示。 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. Among them, Li 10 GeP 2 S 12 faces the cathode material, and 75% Li 2 S-25% P 2 S 5 faces metal lithium. The device structure is shown in Figure 1.
实施例7Example 7
本实施例提供了一种高容量的新型固态电池，电池包括正极，负极和固态电解质。正极按质量比包含45％的TiS 2、15％的S、20％的Li 10GeP 2S 12、10％的石墨烯，10％的碳纳米管。将称好的正极材料各组分在Ar气氛下球磨混合，球磨时间为4小时得到正极材料。 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.
将所制备的正极材料、Li 10GeP 2S 12、75％Li 2S-25％P 2S 5双层固态硫化物电解质以及锂片组装成全固态电池。其中Li 10GeP 2S 12朝向正极材料，75％Li 2S-25％P 2S 5朝向金属锂。器件结构如图1所示。 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. Among them, Li 10 GeP 2 S 12 faces the cathode material, and 75% Li 2 S-25% P 2 S 5 faces metal lithium. The device structure is shown in Figure 1.
实施例8Example 8
本实施例提供了一种高容量的新型固态电池，电池包括正极，负极和固态电解质。正极按质量比包含60％的Mo 6S 8、20％的S、10％的石墨烯，10％的碳纳米管。将称好的正极材料各组分在Ar气氛下球磨混合，球磨时间为4小时，得到正极材料。 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.
将所制备的正极材料、Li 10GeP 2S 12、75％Li 2S-25％P 2S 5双层固态硫化物电解质以及锂片组装成全固态电池。其中Li 10GeP 2S 12朝向正极材料，75％Li 2S-25％P 2S 5朝向金属锂。器件结构如图1所示。图4为发明实施例8提供的新型固态电池和对比例中的固态电池在循环至第20周时的充放电曲线图。 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. Among them, Li 10 GeP 2 S 12 faces the cathode material, and 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.
应用本实施例提供的材料，20周循环的放电比容量远高于应用对比例提供材料的放电比容量。Using the material provided in this embodiment, the specific discharge capacity of the 20-week cycle is much higher than that of the material provided in the comparative example.
实施例9Example 9
本实施例提供了一种高容量的新型固态电池，电池包括正极，负极和固态电解质。正极按质量比包含95％的Mo 6S 8、4％的S、0.5％的石墨烯，0.5％ 的碳纳米管。将称好的正极材料各组分在Ar气氛下球磨混合，球磨时间为4小时，得到正极材料。 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.
将所制备的正极材料、Li 10GeP 2S 12、75％Li 2S-25％P 2S 5双层固态硫化物电解质以及锂片组装成全固态电池。其中Li 10GeP 2S 12朝向正极材料，75％Li 2S-25％P 2S 5朝向金属锂。器件结构如图1所示。 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. Among them, Li 10 GeP 2 S 12 faces the cathode material, and 75% Li 2 S-25% P 2 S 5 faces metal lithium. The device structure is shown in Figure 1.
实施例10Example 10
本实施例提供了一种高容量的新型固态电池，电池包括正极，负极和固态电解质。正极按质量比包含82％的Mo 6S 8、13％的S、2.5％的石墨烯，2.5％的碳纳米管。将称好的正极材料各组分在Ar气氛下球磨混合，球磨时间为4小时，得到正极材料。 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.
将所制备的正极材料、Li 10GeP 2S 12、75％Li 2S-25％P 2S 5双层固态硫化物电解质以及锂片组装成全固态电池。其中Li 10GeP 2S 12朝向正极材料，75％Li 2S-25％P 2S 5朝向金属锂。器件结构如图1所示。 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. Among them, Li 10 GeP 2 S 12 faces the cathode material, and 75% Li 2 S-25% P 2 S 5 faces metal lithium. The device structure is shown in Figure 1.
实施例11Example 11
本实施例提供了一种高容量的新型固态电池，电池包括正极，负极和固态电解质。正极按质量比包含70％的Mo 6S 8、30％的S。将称好的正极材料各组分在Ar气氛下球磨混合，球磨时间为4小时，得到正极材料。 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.
将所制备的正极材料、Li 10GeP 2S 12、75％Li 2S-25％P 2S 5双层固态硫化物电解质以及锂片组装成全固态电池。其中Li 10GeP 2S 12朝向正极材料，75％Li 2S-25％P 2S 5朝向金属锂。器件结构如图1所示。 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. Among them, Li 10 GeP 2 S 12 faces the cathode material, and 75% Li 2 S-25% P 2 S 5 faces metal lithium. The device structure is shown in Figure 1.
实施例12Example 12
本实施例提供了一种高容量的新型固态电池，电池包括正极，负极和固态电解质。正极按质量比包含5％的Mo 6S 8、95％的S。将称好的正极材料各组分在Ar气氛下球磨混合，球磨时间为4小时，得到正极材料。 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.
将所制备的正极材料、Li 10GeP 2S 12、75％Li 2S-25％P 2S 5双层固态硫化物电解质以及锂片组装成全固态电池。其中Li 10GeP 2S 12朝向正极材料，75％Li 2S-25％P 2S 5 朝向金属锂。器件结构如图1所示。 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. Among them, Li 10 GeP 2 S 12 faces the cathode material, and 75% Li 2 S-25% P 2 S 5 faces metal lithium. The device structure is shown in Figure 1.
实施例13Example 13
本实施例提供了一种高容量的新型固态电池，电池包括正极，负极和固态电解质。正极按质量比包含63％的Mo 6S 8、27％的S、5％的Li 10GeP 2S 12、2.5％的石墨烯，2.5％的碳纳米管。将称好的正极材料各组分在Ar气氛下球磨混合，球磨时间为4小时，得到正极材料。 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.
将所制备的正极材料、Li 10GeP 2S 12、75％Li 2S-25％P 2S 5双层固态硫化物电解质以及锂片组装成全固态电池。其中Li 10GeP 2S 12朝向正极材料，75％Li 2S-25％P 2S 5朝向金属锂。器件结构如图1所示。 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. Among them, Li 10 GeP 2 S 12 faces the cathode material, and 75% Li 2 S-25% P 2 S 5 faces metal lithium. The device structure is shown in Figure 1.
实施例14Example 14
本实施例提供了一种高容量的新型固态电池，电池包括正极，负极和固态电解质。正极按质量比包含56％的Mo 6S 8、24％的S、5％的Li 10GeP 2S 12、7.5％的石墨烯，7.5％的碳纳米管。将称好的正极材料各组分在Ar气氛下球磨混合，球磨时间为4小时，得到正极材料。 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.
将所制备的正极材料、Li 10GeP 2S 12、75％Li 2S-25％P 2S 5双层固态硫化物电解质以及锂片组装成全固态电池。其中Li 10GeP 2S 12朝向正极材料，75％Li 2S-25％P 2S 5朝向金属锂。器件结构如图1所示。 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. Among them, Li 10 GeP 2 S 12 faces the cathode material, and 75% Li 2 S-25% P 2 S 5 faces metal lithium. The device structure is shown in Figure 1.
实施例15-实施例28中的电解质、负极种类、器件结构与实施例14相同，区别在于正极材料中过渡金属硫化物混合种类不同。具体见表1。The electrolytes, negative electrode types, and device structures in 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.
实施例29Example 29
本实施例提供了一种高容量的新型固态电池，电池包括正极，负极和固态电解质。正极按质量比包含70％的Mo 6S 8、30％的LiFePO 4。将称好的正极材料各组分在Ar气氛下球磨混合，球磨时间为4小时，得到正极材料。 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.
将所制备的正极材料、Li 10GeP 2S 12、75％Li 2S-25％P 2S 5双层固态硫化物电解质以及锂片组装成全固态电池。其中Li 10GeP 2S 12朝向正极材料，75％Li 2S-25％P 2S 5朝向金属锂。器件结构如图1所示。 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. Among them, Li 10 GeP 2 S 12 faces the cathode material, and 75% Li 2 S-25% P 2 S 5 faces metal lithium. The device structure is shown in Figure 1.
实施例30-实施例36中Mo 6S 8、电解质、负极种类、器件结构与实施例29相同，区别在于正极材料中其他正极材料混合种类、各组分所占比例不同。具体见表1。 The Mo 6 S 8 , electrolyte, negative electrode type, and device structure in 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.
图5为发明实施例36提供的新型固态电池再循环至第20周时的充放电曲线图，比容量按正极总质量计，可达159mAh/g。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.
对比例Comparison
一种全固态锂硫电池，电池包括正极，负极和固态电解质。正极按质量比包含单质硫20％、石墨烯40％，碳纳米管40％。将称好的正极材料各组分在惰性气氛下球磨混合，球磨时间为4小时，得到正极材料。An all-solid-state lithium-sulfur battery. 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.
将所制备的正极材料、Li 10GeP 2S 12、和75％Li 2S-25％P 2S 5双层固态硫化物电解质以及锂片组装成全固态锂硫电池。其中Li 10GeP 2S 12朝向正极材料，75％Li 2S-25％P 2S 5朝向金属锂。器件结构同图1所示。图4中示出了该器件在70℃下的充放电曲线。 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. Among them, Li 10 GeP 2 S 12 faces the cathode material, and 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.
质量以活性物质计，20周放电比容量仅为16mAh/g，质量以正极总质量计，20周放电比容量仅为3.2mAh/g。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.
以上所有实施例充放电电流为15uA，均在70℃下测试。The charging and discharging current of all the above examples is 15uA, and they are all tested at 70°C.
表1:各实施例数据Table 1: Data of each example
Figure PCTCN2020086681-appb-000001
Figure PCTCN2020086681-appb-000001
Figure PCTCN2020086681-appb-000002
Figure PCTCN2020086681-appb-000002
Figure PCTCN2020086681-appb-000003
Figure PCTCN2020086681-appb-000003
表1Table 1
*:表中正极为金属硫化物时，活性物质按金属硫化物质量计；正极含S或Li 2S x时，活性物质按S或Li 2S x质量计；正极含金属硫化物和含锂正极材料时，活性物质按金属硫化物和含锂正极材料总质量计。 *: When the positive electrode in the table is metal sulfide, 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.
本发明提供的新型固态电池中的正极材料含有一类过渡金属硫族化合物，这类过渡金属硫族化合物本身具有电化学活性，可以起到活性物质的作用，此外其具有较好的电子导电性和粒子导电性，可以降低甚至免除正极材料中固态电解质和导电添加剂的引入，可以全部或部分取代电极中的固态电解质和和导电添加剂，从而有效提高电极中电化学活性物质的占比，最终 提高能量密度，使得基于该复合正极的新型固态电池具有能量密度高、安全性好等优点。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.
本发明新型固态电池中正极材料的过渡金属硫化物与硫或一些传统正极材料具有很好地兼容性，相互配合使用时，相互之间电化学/化学稳定性好。以上所述的具体实施方式，对本发明的目的、技术方案和有益效果进行了进一步详细说明，所应理解的是，以上所述仅为本发明的具体实施方式而已，并不用于限定本发明的保护范围，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。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.

Claims (9)

  1. 一种新型固态电池，其特征在于，所述新型固态电池包括嵌入式储锂的正极、电池电解质以及富锂负极；A novel solid-state battery, characterized in that, the novel solid-state battery includes an embedded lithium-storing positive electrode, a battery electrolyte, and a lithium-rich negative electrode;
    所述嵌入式储锂的正极包括：包含嵌入式储锂的过渡金属硫族化合物及其复合材料的正极材料；所述正极材料同时具备离子导电性和电子导电性，并且在所述正极内部构成三维离子、电子导电网络结构，所述网络结构用以锂离子嵌入和脱出；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;
    所述过渡金属硫族化合物的晶体结构包括层状结构或谢弗雷尔相，所述过渡金属硫族化合物中的过渡金属包括IVB，VB，VIB，VIIB族金属元素中的至少一种；在所述锂离子嵌入和脱出过程中，所述过渡金属发生变价反应。The crystal structure of the transition metal chalcogenide compound includes a layered structure or a Schefferer 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.
  2. 根据权利要求1所述的新型固态电池，其特征在于，所述金属硫族化合物具体为M xS y，M为阳离子，包括：Mo,Ti,V,Cr,Mn,Nb,Zr,W,Re,Ta，Re中的一种或多种；1≤x≤9，1≤y≤9，且x、y的取值满足保持化合物电中性。 The novel solid-state battery according to claim 1, wherein the metal chalcogenide compound is specifically M x S y , and M is a cation, including: Mo, Ti, V, Cr, Mn, Nb, Zr, W, One or more of Re, Ta, Re; 1≤x≤9, 1≤y≤9, and the values of x and y satisfy the need to keep the compound electrically neutral.
  3. 根据权利要求1所述的新型固态电池，其特征在于，所述正极材料还包括：与所述嵌入式储锂的过渡金属硫族化合物及其复合材料混合的S,Li 2S 8,Li 2S 4,Li 2S 2,Li 2S,LiFePO 4,LiMn 2O 4,LiCoO 2,LiNi 0.5Mn 1.5O 4,LiNi 0.5Mn 0.5O 2,LiNiO 2,LiNi 1/3Co 1/3Mn 1/3O 2,LiNi 0.5Co 0.3Mn 0.2O 2,LiNi 0.6Co 0.2Mn 0.2O 2,LiNi 0.8Co 0.1Mn 0.1O 2,LiNiCoAlO 2,Li 4Ti 5O 12中的一种或多种正极材料。 The new solid-state battery according to claim 1, wherein the cathode material further comprises: S, Li 2 S 8 , Li 2 mixed with the transition metal chalcogenide compound for embedded lithium storage and its composite material S 4 , Li 2 S 2 , Li 2 S, LiFePO 4 , LiMn 2 O 4 , LiCoO 2 , LiNi 0.5 Mn 1.5 O 4 , LiNi 0.5 Mn 0.5 O 2 , LiNiO 2 , LiNi 1/3 Co 1/3 Mn 1 /3 O 2 , LiNi 0.5 Co 0.3 Mn 0.2 O 2 , LiNi 0.6 Co 0.2 Mn 0.2 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 , LiNiCoAlO 2 , Li 4 Ti 5 O 12 , one or more of the cathode materials .
  4. 根据权利要求1所述的新型固态电池，其特征在于，所述正极还包括：占正极质量0～30％的固态电解质和0％～30％的碳材料。The novel solid-state battery according to claim 1, wherein the positive electrode further comprises: 0-30% of the mass of the positive electrode solid electrolyte and 0%-30% carbon material.
  5. 根据权利要求1所述的新型固态电池，其特征在于，所述复合材料中，过渡金属硫族化合物所占的质量百分比为5％～100％。The novel solid-state battery according to claim 1, wherein the mass percentage of the transition metal chalcogenide compound in the composite material is 5%-100%.
  6. 根据权利要求4所述的新型固态电池，其特征在于，所述碳材料包 括Super-P炭黑、碳纤维、碳纳米管、石墨烯、乙炔黑中的一种或多种。The novel solid-state battery according to claim 4, wherein the carbon material includes one or more of Super-P carbon black, carbon fiber, carbon nanotube, graphene, and acetylene black.
  7. 根据权利要求1所述的新型固态电池，其特征在于，所述电池电解质为固态的电解质，设置于正极和负极之间，所述电池电解质含有锂超离子导体材料。The novel solid-state battery according to claim 1, wherein the battery electrolyte is a solid electrolyte, which is arranged between the positive electrode and the negative electrode, and the battery electrolyte contains a lithium superion conductor material.
  8. 根据权利要求1所述的新型固态电池，其特征在于，所述富锂负极具体为：包含集流体的金属锂、锂合金、锂碳或硅基材料，所述硅基材料为预嵌锂的硅基材料。The novel solid-state battery according to claim 1, wherein the lithium-rich negative electrode is specifically: metal lithium, lithium alloy, lithium carbon or silicon-based material containing a current collector, and the silicon-based material is pre-inserted with lithium Silicon-based materials.
  9. 一种上述权利要求1所述的新型固态电池中的正极材料，其特征在于，所述正极材料包括嵌入式储锂的过渡金属硫族化合物及其复合材料；所述正极材料同时具备离子导电性和电子导电性，并且在所述正极内部构成三维离子、电子导电网络结构，所述网络结构用以锂离子嵌入和脱出；A positive electrode material in a novel solid-state battery according to claim 1, wherein the positive electrode material includes transition metal chalcogenides embedded in lithium storage and their composite materials; the positive electrode material also has 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 insertion and extraction of lithium ions;
    所述过渡金属硫族化合物的晶体结构包括层状结构或谢弗雷尔相，所述过渡金属硫族化合物中的过渡金属包括IVB，VB，VIB，VIIB族金属元素中的至少一种；在所述锂离子嵌入和脱出过程中，所述过渡金属发生变价反应。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.
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