WO2019019407A1 - Électrode contenant du lithium, son procédé de préparation et batterie au lithium la comprenant - Google Patents

Électrode contenant du lithium, son procédé de préparation et batterie au lithium la comprenant Download PDF

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Publication number
WO2019019407A1
WO2019019407A1 PCT/CN2017/105654 CN2017105654W WO2019019407A1 WO 2019019407 A1 WO2019019407 A1 WO 2019019407A1 CN 2017105654 W CN2017105654 W CN 2017105654W WO 2019019407 A1 WO2019019407 A1 WO 2019019407A1
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Prior art keywords
lithium
battery
electrode
carbon
positive electrode
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PCT/CN2017/105654
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English (en)
Chinese (zh)
Inventor
刘承浩
陈立桅
卢威
沈炎宾
王亚龙
康拓
郭峰
陈鹏
Original Assignee
中能中科（天津）新能源科技有限公司
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Priority claimed from CN201710617871.1A external-priority patent/CN109309205A/zh
Priority claimed from CN201710618561.1A external-priority patent/CN109309195A/zh
Priority claimed from CN201710618423.3A external-priority patent/CN109309206A/zh
Priority claimed from CN201710617327.7A external-priority patent/CN109309202A/zh
Priority claimed from CN201710684880.2A external-priority patent/CN109390556A/zh
Application filed by 中能中科（天津）新能源科技有限公司 filed Critical 中能中科（天津）新能源科技有限公司
Publication of WO2019019407A1 publication Critical patent/WO2019019407A1/fr

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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
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • 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

Definitions

  • the present invention relates to the field of battery technology, and in particular, to a lithium-containing electrode, a preparation method thereof and an application thereof.
  • Lithium batteries have high energy density, good cycle stability, safety, etc.
  • the lithium batteries currently used are mainly lithium ion batteries.
  • Lithium-ion batteries are widely used in communications, electric vehicles, energy storage, etc. due to their high specific energy, high battery voltage, wide operating range and long storage life.
  • the negative electrode is one of the four major components of the lithium ion battery (positive electrode, negative electrode, separator and electrolyte).
  • Most of the negative electrode materials used on the market today are graphite materials, which are inexpensive and safe.
  • the specific capacity of the material is low (372 mAh/g), and the cycle life is generally low, and the rate performance is poor, which limits the development of the battery to higher performance.
  • the metal lithium negative electrode has the most negative electrode potential (-3.04 vs standard hydrogen electrode), high mass specific capacity (3860 mAh/g), and low density (lightest metal) has been attracting attention.
  • metal lithium is preferentially deposited in some parts to form dendrites (lithium dendrites).
  • lithium dendrites will pierce the solid electrolyte on the surface of metallic lithium.
  • the layer (SEI) reacts with the electrolyte, consuming electrolyte to cause battery failure, and on the other hand consuming metal lithium, resulting in low coulombic efficiency.
  • lithium dendrites may pierce the diaphragm, causing a short circuit in the battery, causing safety problems.
  • One of the main objects of the present invention is to provide a lithium-containing electrode, a preparation method thereof and an application thereof, which can be used for suppressing lithium dendrite growth and prolonging battery cycle life.
  • a lithium-containing electrode comprising a current collector and an electrode material layer having a lithium carbon composite material as an active material attached to a surface of the current collector, the electrode material layer being micro-nanoscale
  • the metal lithium-skeletal carbon composite material is composed of, or the electrode material layer comprises a micro-nano-scale lithium alloy-skeletal carbon composite material.
  • a method of preparing the above lithium-containing electrode comprising: attaching a lithium carbon composite material dispersed on a surface of a current collector to a surface of a current collector to form a lithium carbon composite material layer by applying pressure Electrode material layer;
  • a slurry containing a lithium carbon composite material is coated on the surface of the current collector and then dried to form an electrode material layer containing the lithium carbon composite material.
  • a lithium ion battery comprising the lithium-containing electrode described above as a battery negative electrode.
  • a lithium sulfur battery comprising the above lithium-containing electrode as a battery negative electrode.
  • a lithium oxygen battery comprising the above lithium-containing electrode as a battery negative electrode.
  • a primary or secondary lithium battery comprising the lithium-containing electrode described above as a battery negative.
  • an all-solid lithium battery that includes the lithium-containing electrode described above as a battery negative.
  • Lithium-carbon composite material is composed of micro-nano-sized particles.
  • the large specific surface area of the particles effectively increases the specific surface area of the lithium negative electrode, reduces the surface current density of the lithium negative electrode, can effectively inhibit the growth of lithium dendrites, and prolong the circulation of lithium-ion batteries. Lifetime increases the coulombic efficiency of the battery.
  • the mass of the lithium-carbon composite material (powder material) per unit area can be flexibly adjusted, and the capacity per unit area of the negative electrode can be adjusted. Avoiding the high positive and negative electrode capacity ratio due to difficulty in preparing thin metal lithium, resulting in wasted anode capacity.
  • Example 1 is a charge and discharge cycle capacity retention diagram and a Coulomb efficiency diagram of a battery in Example 1;
  • Example 2 is a charge and discharge cycle capacity retention diagram and a coulombic efficiency diagram of the battery in Example 2;
  • Example 3 is a charge and discharge cycle capacity retention diagram and a Coulomb efficiency diagram of the battery in Example 3;
  • Example 4 is a charge and discharge cycle capacity retention diagram and a Coulomb efficiency diagram of the battery in Example 4;
  • Example 5 is a charge and discharge cycle capacity retention diagram and a coulombic efficiency diagram of the battery in Example 5;
  • Example 6 is a charge and discharge cycle capacity retention diagram and a coulombic efficiency diagram of the battery in Example 6;
  • Fig. 7 is a graph showing the charge and discharge cycle capacity retention and the coulombic efficiency of the battery of Example 7.
  • Fig. 8 is a graph showing the charge and discharge cycle capacity retention and the coulombic efficiency of the battery of Example 8.
  • Fig. 9 is a graph showing the charge and discharge cycle capacity retention and the coulombic efficiency of the battery of Example 9.
  • Fig. 10 is a graph showing the charge and discharge cycle capacity retention and the coulombic efficiency of the battery in Example 10.
  • Fig. 11 is a graph showing the capacity retention of the battery in the eleventh embodiment.
  • Figure 12 is a graph showing the capacity retention of the battery in Example 12.
  • Fig. 13 is a graph showing the capacity retention of the battery in the thirteenth embodiment.
  • Fig. 14 is a graph showing the capacity retention of the battery in the fourteenth embodiment.
  • Fig. 15 is a graph showing the capacity retention of the battery in the fifteenth embodiment.
  • Fig. 16 is a graph showing the capacity retention of the battery in the sixteenth embodiment.
  • Figure 17 is a graph showing the charge and discharge curves of the first and sixth cycles of the battery in Example 17.
  • Figure 18 is a graph showing the battery capacity retention in Example 17.
  • Figure 19 is a graph showing the first and fifth cycles of charge and discharge of the battery in Example 18.
  • Figure 20 is a graph showing the battery capacity retention in Example 18.
  • Figure 21 is a graph showing the charge and discharge curves of the first and seventh cycles of the battery in Example 19.
  • Figure 22 is a graph showing the battery capacity retention curve in Example 19.
  • Figure 23 is a graph showing a specific capacity voltage curve of a constant current discharge of a battery in Example 20.
  • Figure 24 is a capacity retention curve of the battery in Example 21.
  • Figure 25 is a graph showing a specific capacity voltage curve of a constant current discharge of a battery in Example 22.
  • Figure 26 is a graph showing a specific capacity voltage curve of a constant current discharge of a battery in Example 23.
  • Figure 27 is a capacity retention curve of the battery in Example 24.
  • Figure 28 is a capacity retention curve of the battery in Example 25.
  • Figure 29 is a diagram showing the cycle of the battery in Example 26 as shown below.
  • Figure 30 is a diagram showing the cycle of the battery in Example 27 as shown below.
  • Figure 31 is a diagram showing the cycle of the battery in Example 28 as shown below.
  • One aspect of the present invention provides a lithium-containing electrode, the electrode comprising a current collector and an electrode material layer having a lithium carbon composite material as an active material attached to a surface of the current collector, the electrode material layer being composed of a micro-nano metal A lithium-skeletal carbon composite material composition, or the electrode material layer comprises a micro-nanoscale lithium alloy-skeletal carbon composite material.
  • the metal lithium-skeletal carbon composite material and the lithium alloy-skeletal carbon composite material are collectively referred to as a lithium carbon composite material.
  • the current collector is composed of a metal foil, which may include copper foil, nickel foil, or the like.
  • the metal foil may have a thickness in the range of 6-20 microns and a surface roughness of Ra 0.2-0.38.
  • the current collector is comprised of a porous metal material.
  • the porous metal material may include metal foam, punched metal, metal mesh, and the like.
  • the metal foam may include copper foam, nickel foam, iron foam, and foamed alloys such as iron foam nickel and copper foam nickel.
  • the thickness of the metal foam can be in the range of 10-300 um, the porosity can be in the range of 30-85%, and the pore size distribution can be 10-150 PPI, depending on the metal foam material.
  • a perforated metal can be used to form the current collector.
  • the punched metal may include a punched copper foil or the like.
  • the current collector can be in the form of a metal mesh.
  • the current collector can be a copper mesh and the mesh can range from 100 to 400 mesh.
  • the areal density (mass per unit area of the current collector surface) of the lithium carbon composite in the lithium-containing electrode may be 5-30 mg/cm 2 , preferably 15-25 mg/cm 2 .
  • the lithium carbon composite material is a micro-nano-sized particle or powder having a particle size of from 20 nanometers to 100 micrometers comprising a porous carbon material support and metallic lithium or lithium present in and on the pores of the porous carbon material support. alloy.
  • the content of metallic lithium or lithium alloy in the lithium carbon composite may be 10% to 95% by mass, for example, 10-80%, 20-70%, 50%-60%, and the like.
  • the porous carbon material support may include at least one of carbon fiber microspheres, porous carbon nanotube microspheres, and acetylene black.
  • the porous carbon material carrier is a porous carbon nanotube microsphere, which is a microsphere formed by intertwining a carbon nanotube with each other and having nanometer-scale pores inside and on the surface, the particle diameter of the microsphere is 1. -100 microns.
  • Such microspheres have an approximately solid structure (like a wool-like structure), that is, the inside of the microspheres is filled with carbon nanotubes or carbon nanofibers, but nano-scale pores exist between the entangled agglomerated carbon nanotubes or carbon nanofibers, and these pores Can be used to hold metallic lithium particles.
  • the carbon nanotube microspheres are spherical or spheroidal particles having an average diameter of from 1 ⁇ m to 100 ⁇ m, preferably from 1 ⁇ m to 25 ⁇ m; and a specific surface area of from 100 to 1500 m 2 /g, preferably from 150 to 500 m 2 / g; the pore size distribution of the pores contained in the microspheres may be from 1 to 200 nm, preferably from 1 to 50 nm.
  • the carbon nanotube microspheres have at least any one of a microscopic spherical solid aggregate structure, a spherical aggregate structure, a spheroidal aggregate structure, a porous spherical aggregate structure, and a doughnut-shaped aggregate structure.
  • the carbon nanotubes comprise any one or a combination of two or more of multi-walled carbon nanotubes, double-walled carbon nanotubes, and single-walled carbon nanotubes, optionally subjected to surface functionalization. deal with.
  • the group modified on the surface of the carbon nanotube may be selected from, but not limited to, a group such as -COOH, -OH, -NH 2 or the like.
  • the carbon nanotube microspheres can be prepared by dispersing the carbon nanotubes in a solvent to form a dispersion, followed by spray drying.
  • the preparation method may include the following steps:
  • the carbon nanotubes are dispersed by ultrasonic treatment into a dispersion solvent (without a surfactant) to obtain a dispersion;
  • step B The dispersion obtained in the step A is sprayed through the nozzle of the spray dryer, and the inlet air temperature and the outlet air temperature are preset, and the solution is kept in a stirring state during the spraying process;
  • Cooling that is, obtaining carbon nanotube microspheres.
  • the solvent employs an organic and/or inorganic liquid capable of uniformly dispersing carbon nanotubes/carbon nanofibers and nanocarbon particles, for example, water, ammonia, hydrochloric acid solution, ethanol, acetone, isopropanol. Any combination of one or more.
  • an organic and/or inorganic liquid capable of uniformly dispersing carbon nanotubes/carbon nanofibers and nanocarbon particles, for example, water, ammonia, hydrochloric acid solution, ethanol, acetone, isopropanol. Any combination of one or more.
  • the solvent may be a mixture of ethanol and water in a volume ratio of 1:10.
  • the conditions of spray drying may include: an inlet air temperature of 150 to 250 ° C, an outlet air temperature of 75 ° C or higher, such as 75 to 150 ° C, or 90 ° C or higher; a preferred spray drying condition includes: The inlet air temperature is 190 to 210 ° C, and the outlet air temperature is 90 to 110 ° C.
  • the spray rate at spray drying can range from 1 milliliter per minute to 100 liters per minute.
  • the porous carbon material support is carbon fiber microspheres having a morphology and structure similar to carbon nanotube microspheres and can be prepared by a similar spray drying process.
  • the porous carbon material carrier is acetylene black
  • the acetylene black used is obtained by pyrolyzing acetylene gas at a high temperature to isolate the air for thermal cracking, and has a particle diameter of 20 to 100 nm, preferably 70 to 80 nm; It is 120 to 200 m 2 /g, and preferably 140 to 160 m 2 /g.
  • the lithium carbon composite may be obtained by mixing molten metal with a porous carbon skeleton material and cooling.
  • the mixing may include stirring and mixing the metallic lithium with the porous carbon skeleton material under heating (for example, about 200 ° C) or immersing the porous carbon skeleton material in the molten metallic lithium.
  • the preparation of the lithium carbon composite is carried out in an inert atmosphere, for example in a glove box in an argon atmosphere (water content ⁇ 10 ppm, oxygen content ⁇ 10 ppm).
  • the lithium carbon composite is subjected to a screening step prior to use.
  • a 50-100 mesh standard screen is passed through an argon-protected glove box to collect the lithium carbon composite through the mesh.
  • the lithium carbon composite is a lithium alloy-skeletal carbon composite formed of metallic lithium and one or more elements selected from the group consisting of magnesium, silicon, boron, carbon, Nitrogen, oxygen, fluorine, aluminum, phosphorus, sulfur, chlorine, calcium, zinc, gallium, antimony, arsenic, selenium, bromine, antimony, bismuth, palladium, silver, cadmium, indium, tin, antimony, bismuth, iodine, antimony, Platinum, gold, mercury, antimony, lead, antimony and antimony.
  • elements selected from the group consisting of magnesium, silicon, boron, carbon, Nitrogen, oxygen, fluorine, aluminum, phosphorus, sulfur, chlorine, calcium, zinc, gallium, antimony, arsenic, selenium, bromine, antimony, bismuth, palladium, silver, cadmium, indium, tin, antimony, bismuth, iodine, antimony, Platinum, gold, mercury, antimony, lead, antimony and
  • the weight percentage of lithium in the lithium alloy is from 70% to 99.9%.
  • the lithium alloy may include a lithium ternary alloy such as lithium magnesium aluminum, lithium gold silver ternary alloy, lithium four alloys, such as a lithium alloy, such as a lithium magnesium alloy, a lithium silicon alloy, or the like.
  • a meta-alloy such as lithium magnesium aluminum tin, a lithium gold silver platinum quaternary alloy, and the like.
  • the weight percentage of the additional various elements is 0.1 to 30% by weight, preferably 0.5, based on the total weight of the lithium alloy. -20% by weight, and more preferably 1-10% by weight.
  • the lithium alloy is a lithium magnesium alloy, a lithium silicon alloy, a lithium aluminum alloy, a lithium boron alloy, a lithium indium alloy, and other multivariate derivatives.
  • a lithium alloy-skeletal carbon composite can be prepared by the following method:
  • Another aspect of the present invention provides a method of preparing the above lithium-containing electrode, comprising: attaching a lithium carbon composite material dispersed on a surface of a current collector to a surface of a current collector by applying pressure to form a lithium carbon composite material layer as an electrode material
  • the layer, or a slurry containing a lithium carbon composite is coated on the surface of the current collector and then dried to form an electrode material layer containing the lithium carbon composite.
  • the electrode pole piece can be obtained in one step by simply laminating the lithium carbon composite material on the current collector.
  • the lithium carbon composite material uniformly distributed on the surface of the current collector can be pressure-compressed to the current collector by manual or mechanical pressurization.
  • Mechanical pressurization may include the use of a roller press or a static press or the like.
  • the pressure at the time of pressure recombination may range from 30 KPa to 30 MPa.
  • a coating material is used to form an electrode material layer comprising the lithium carbon composite, comprising:
  • anhydrous solvent means a water content of ⁇ 50 ppm
  • the slurry obtained in the step (1) is coated on the surface of the current collector, and then dried to form a coating layer containing the lithium carbon composite material.
  • Steps (1) and (2) are carried out in an inert atmosphere, for example, in an argon-protected glove box (water content ⁇ 10 ppm, oxygen content ⁇ 10 ppm) or in a dry room (dew point below -40 ° C) get on.
  • an inert atmosphere for example, in an argon-protected glove box (water content ⁇ 10 ppm, oxygen content ⁇ 10 ppm) or in a dry room (dew point below -40 ° C) get on.
  • the binder may be a mixture of styrene butadiene rubber and polystyrene (the mass ratio of the two may be 1:1), polyvinylidene fluoride (PVDF) or other oily solvent, etc., which makes lithium carbon Between the composite particles, the lithium carbon composite and the current collector are bonded together.
  • the styrene-butadiene rubber may have a molecular weight of 2 million and the polystyrene may have a melt index of 6 g/min (200 ° C / 5 kg).
  • the mass ratio of the binder (styrene-butadiene rubber and polystyrene) to the lithium-carbon composite material may be 5 to 10:95 to 90.
  • the solvent may be p-xylene or the like for dissolving the binder while uniformly mixing the binder with the lithium carbon composite.
  • the mass ratio of the solvent to the binder and the lithium carbon composite dispersed therein may be from 10 to 15:1.
  • a slurry containing a lithium carbon composite can be applied to the surface of the current collector by electrostatic spraying, knife coating, painting, spin coating, and dispensing.
  • the invention also provides the use of the lithium-containing electrode described above.
  • a lithium-containing electrode can be used as a negative electrode of a lithium ion battery.
  • a lithium ion battery refers to a battery composed of a lithium storage compound as a positive and negative electrode material, and lithium ions are exchanged between the positive and negative electrodes during battery cycling. Accordingly, another aspect of the present invention provides a lithium ion battery including the above-described lithium-containing electrode as a battery negative electrode.
  • the positive electrode of the lithium ion battery may include lithium cobaltate, lithium iron phosphate, lithium manganate, lithium titanate, Ni-Co-Mn, or Ni-Co-Al ternary material or the like as a positive electrode active material.
  • a lithium-containing electrode can be used as a negative electrode of a lithium-sulfur battery.
  • the positive electrode of the lithium sulfur battery may include a composite material of elemental sulfur and elemental sulfur and an inorganic carbon material or an organic material as an active electrode material.
  • the inorganic carbon material used for the positive electrode of the lithium sulfur battery includes at least one of carbon aerogel, graphene, and activated carbon; and the organic material used includes polyacrylonitrile (PAN).
  • PAN polyacrylonitrile
  • a composite of elemental sulfur and an inorganic carbon material or an organic material is used, wherein the elemental sulfur content is 50-85% by mass.
  • a lithium-containing electrode can be used as a negative electrode of a lithium-oxygen battery.
  • the positive electrode of the lithium oxygen battery includes a current collector and a porous carbon material attached to the surface of the current collector.
  • the porous carbon material is at least one of carbon fiber, carbon nanotube, acetylene black, activated carbon or mesoporous carbon.
  • the active material film is prepared by coating a positive electrode slurry coating on a substrate (for example, a glass plate), and the active material film has a thickness of 100 to 150 ⁇ m. Then, the active material film was pressed against the current collector to prepare a positive electrode tab, and the applied pressure was 10-15 MPa.
  • the positive electrode slurry can be prepared by mixing a porous carbon material, a binder, and a solvent.
  • the binder may be polyvinylidene fluoride, an aqueous binder LA132, or an aqueous binder LA133, and the solvent may be at least one of N-methylpyrrolidone, tetrahydrofuran, and water.
  • the mass ratio of the porous carbon material to the binder in the positive electrode slurry may be from 1:1 to 1.5.
  • the cathode current collector may be made of aluminum foil, porous metal material, or carbon paper.
  • the porous metal material is the same as the porous metal material of the anode current collector, and may include a metal foam, a metal mesh, and a punched metal, preferably foamed nickel or foamed iron.
  • a lithium oxygen battery is obtained by arranging the components in the following order: positive electrode tab/separator/electrolyte/negative pole tab.
  • the membrane can be a fiberglass membrane, a porous polypropylene (PP) membrane, or a porous polyethylene (PE) membrane.
  • PP polypropylene
  • PE porous polyethylene
  • the various components of the lithium-oxygen battery are placed in a housing that is an open system that can take in oxygen from the outside environment.
  • a lithium-containing electrode can be used as a negative electrode of a lithium primary battery.
  • the positive electrode of the lithium primary battery is a soluble positive electrode (liquid or gas) or a solid positive electrode.
  • the soluble positive electrode of the lithium primary battery may include one of the following components as the positive electrode active material: sulfur dioxide, thionyl chloride, and sulfuryl chloride.
  • the electrolyte can be selected to match the corresponding positive active material.
  • a positive electrode active material/electrolyte combination may be employed: sulfur dioxide (electrolyte: lithium bromide, acetonitrile); thionyl chloride (electrolyte: LiAlCl 4 , SOCl 2 ); sulfuryl chloride (electrolyte: LiAlCl 4 , SO 2 Cl 2 ) ).
  • the solid positive electrode of the lithium primary battery may include one of the following components as a positive electrode active material: manganese dioxide, a carbon fluoride polymer, iron disulfide, copper oxide, iodine, copper sulfide, silver chromate, and vanadium. Silver acetate.
  • lithium salts for the electrolyte used for the lithium primary battery solid positive electrode, a combination of one or more of the following lithium salts and the following solvents may be employed:
  • Lithium salt LiClO 4 (lithium perchlorate), LiBr (lithium bromide), LiI (lithium iodide), LiAlCl 4 (lithium high aluminate), LiPF 6 (lithium hexafluorophosphate), LiTFSI (bistrifluoromethylsulfonimide) Lithium or lithium bis(trifluoromethanesulfonate) imide);
  • Solvent acetonitrile, ⁇ -butyrolactone, dimethyl sulfoxide, dimethyl sulfite, 1,2-dimethyl ethane, dioxolane, methyl formate, propylene carbonate and tetrahydrofuran.
  • a lithium-containing electrode can be used as a negative electrode of a lithium secondary battery.
  • the positive electrode of the lithium secondary battery is a lithium-free positive electrode.
  • the lithium-free positive electrode of the lithium secondary battery includes one of the following components as a positive electrode active material: manganese dioxide and vanadium oxide.
  • the manganese dioxide comprises manganese dioxide of the following phases: ⁇ -MnO 2 , ⁇ -MnO 2 , ⁇ -MnO 2 or ⁇ -MnO 2 ;
  • the vanadium oxide comprises one of the following: V 2 O 5 , VO 2 , V 6 O 13 , manganese/copper/silver doped vanadium oxide.
  • the primary/secondary lithium battery consists of the negative electrode described above, the positive electrode described above, and an electrolyte, a separator.
  • the membrane may be polypropylene/polyethylene (PP/PE), porosity: 33-48 thickness: 10-40 microns.
  • a lithium-containing electrode can be used as a negative electrode of an all-solid lithium battery.
  • the positive electrode of the all-solid lithium battery includes some lithium-containing positive electrodes, such as lithium cobaltate, lithium iron phosphate, nickel cobalt aluminum, nickel cobalt manganese ternary materials, and the like; For example: vanadium pentoxide, manganese dioxide, and the like.
  • the positive electrode further contains activated carbon, acetylene black or the like as a conductive agent, and PVDF (polyvinylidene fluoride) or the like as a binder.
  • the positive electrode can be obtained by coating a positive electrode slurry on a current collector and then drying.
  • the positive electrode slurry contains a solvent such as NMP (N-methylpyrrolidone), tetrahydrofuran, water or the like in addition to the above components.
  • the solid electrolyte of the all-solid lithium battery may be selected from the group consisting of: (1) Li 2 SP 2 S 5 series; (2) Li 10 GeP 2 S 12 ; (3) PEO (polyethylene oxide) + Lithium salt, etc.
  • a lithium-containing electrode comprising a current collector and an electrode material layer with a lithium carbon composite material as an active material attached to a surface of a current collector, the electrode material layer being composed of micro-nano-sized metal lithium a skeleton carbon composite composition, or the electrode material layer comprises a micro-nanoscale lithium alloy-skeletal carbon composite.
  • Embodiment 2 is the electrode according to Embodiment 1, wherein the current collector is composed of a porous metal material or a metal foil.
  • Embodiment 3 is the electrode according to Embodiment 2, wherein the porous metal material comprises a metal foam, a punched metal, and a metal mesh; and/or the metal foil comprises a copper foil and a nickel foil.
  • Embodiment 4 is the electrode according to Embodiment 3, wherein the metal foam comprises copper foam, nickel foam, iron foam, nickel iron foam, and copper nickel foam.
  • the lithium carbon composite material comprises a porous carbon material carrier and metal lithium present in and on the pores of the porous carbon material carrier Or lithium alloy.
  • Embodiment 8 is the electrode according to Embodiment 6, wherein the porous carbon material comprises at least one of carbon fiber microspheres, porous carbon nanotube microspheres, and acetylene black.
  • Embodiment 9 is the electrode according to Embodiment 8, wherein the porous carbon nanotube microspheres are microspheres formed by intertwining and agglomerating carbon nanotubes with nanometer-scale pores on the inner and surface, micro The ball has a particle size of 1-100 microns.
  • the pores of the carbon nanotube microspheres have a pore diameter of 1 to 200 nm;
  • the carbon nanotube microspheres have at least one of a microscopic spherical solid aggregate structure, a spherical aggregate structure, a spherical aggregate structure, a porous spherical aggregate structure, and a doughnut aggregate structure;
  • the carbon nanotubes include any one or a combination of two or more of multi-walled carbon nanotubes, double-walled carbon nanotubes, and single-walled carbon nanotubes, optionally subjected to surface functionalization deal with.
  • Embodiment 11 is the electrode according to Embodiment 8, wherein the acetylene black is obtained by pyrolyzing acetylene gas at high temperature isolation air.
  • the embodiment 12 is the electrode according to the specific embodiment 11, wherein the acetylene black has a specific surface area of 120-200 m 2 /g;
  • the acetylene black has a particle size of 20-100 nm
  • the acetylene black is spherical or nearly spherical.
  • the lithium alloy is formed of metallic lithium and one or more elements selected from the group consisting of magnesium, silicon, and boron. , carbon, nitrogen, oxygen, fluorine, aluminum, phosphorus, sulfur, chlorine, calcium, zinc, gallium, antimony, arsenic, selenium, bromine, antimony, bismuth, palladium, silver, cadmium, indium, tin, antimony, antimony, iodine , antimony, platinum, gold, mercury, antimony, lead, antimony and antimony.
  • Embodiment 14 is the electrode according to Embodiment 13, wherein the weight percentage of lithium in the lithium alloy is 70% to 99.9%.
  • Embodiment 15 is the electrode according to the embodiment 13 or 14, wherein the lithium alloy is a lithium magnesium alloy, a lithium silicon alloy, a lithium aluminum alloy, a lithium boron alloy or a lithium indium alloy.
  • the lithium alloy is a lithium magnesium alloy, a lithium silicon alloy, a lithium aluminum alloy, a lithium boron alloy or a lithium indium alloy.
  • the embodiment 16 is a method of preparing the electrode according to any one of the embodiments 1-15, the method comprising: attaching a lithium carbon composite material dispersed on a surface of the current collector to the set by applying pressure Forming a lithium carbon composite material layer on the surface of the fluid as an electrode material layer;
  • a slurry containing a lithium carbon composite material is coated on the surface of the current collector and then dried to form an electrode material layer containing the lithium carbon composite material.
  • Embodiment 17 is the method of embodiment 16 wherein the applied pressure is by manual or mechanical press (e.g., using a roller press or a static press).
  • Embodiment 18 is the method of embodiment 16 or 17, wherein the pressure is from 30 KPa to 30 MPa.
  • the embodiment 19 is a lithium ion battery comprising the electrode according to any one of the embodiments 1-15 as a battery negative electrode.
  • Embodiment 20 is the lithium ion battery according to Embodiment 19, wherein the positive electrode of the lithium ion battery comprises lithium cobaltate, lithium iron phosphate, lithium manganate, lithium titanate, Ni-Co-Mn or Ni- A Co-Al ternary material is used as a positive electrode active material.
  • the embodiment 21 is a lithium-sulfur battery, wherein the lithium-sulfur battery includes the negative electrode according to any one of embodiments 1-15.
  • Embodiment 22 is the lithium-sulfur battery according to Embodiment 21, wherein the positive electrode of the lithium-sulfur battery comprises a composite material of elemental sulfur and elemental sulfur and an inorganic carbon material or an organic material as an active electrode material.
  • the inorganic carbon material comprises at least one of carbon aerogel, graphene and activated carbon; and the organic material comprises polyacrylonitrile.
  • the embodiment 25 is a lithium-oxygen battery, wherein the lithium-oxygen battery includes the negative electrode according to any one of the embodiments 1-15.
  • Embodiment 26 is the lithium oxygen battery according to Embodiment 25, wherein the positive electrode of the lithium oxygen battery is composed of a current collector and a porous carbon material attached to a surface of the current collector.
  • porous carbon material comprises at least one of carbon fiber, carbon nanotube, acetylene black, activated carbon, and mesoporous carbon.
  • the positive electrode slurry contains a porous carbon material, a binder, and a solvent, and is then produced by pressurizing the active material film onto a current collector.
  • FIG. 32 is a lithium oxygen battery according to embodiment 31, wherein the components of the lithium oxygen battery are placed in a housing, the housing being an open system.
  • the present invention is a lithium primary battery, wherein the lithium primary battery includes the negative electrode according to any one of the embodiments 1-15.
  • the lithium primary battery according to the embodiment 33 wherein the positive electrode of the lithium primary battery is a soluble positive electrode or a solid positive electrode.
  • the soluble positive electrode comprises one of the following components as a positive electrode active material: sulfur dioxide, thionyl chloride, and sulfuryl chloride;
  • the solid positive electrode includes one of the following components;
  • the positive electrode active material manganese dioxide, a carbon fluoride polymer, iron disulfide, copper oxide, iodine, copper sulfide, silver chromate, and silver vanadate.
  • the present invention is a lithium secondary battery, wherein the lithium secondary battery includes the negative electrode according to any one of the embodiments 1-15.
  • the lithium secondary battery according to the embodiment 36 wherein the positive electrode of the lithium secondary battery is a lithium-free positive electrode.
  • the lithium secondary battery according to the embodiment 37, wherein the lithium-free positive electrode comprises one of the following components as a positive electrode active material: manganese dioxide and vanadium oxide.
  • the manganese dioxide comprises manganese dioxide of the following phases: ⁇ -MnO 2 , ⁇ -MnO 2 , ⁇ -MnO 2 or ⁇ -MnO 2 ;
  • the vanadium oxide comprises one of the following: V 2 O 5 , VO 2 , V 6 O 13 , manganese/copper/silver doped vanadium oxygen compound.
  • the embodiment 40 is an all-solid-state lithium battery, wherein the all-solid lithium battery includes the anode according to any one of the embodiments 1-15.
  • the embodiment is the all-solid-state lithium battery according to the embodiment 40, wherein the positive electrode of the all-solid lithium battery comprises the following electrode active materials: lithium cobaltate, lithium iron phosphate, nickel cobalt aluminum ternary material, nickel cobalt Manganese ternary material, vanadium pentoxide or manganese dioxide.
  • the embodiment 42 is the all-solid-state lithium battery according to the embodiment 40 or 41, wherein the solid electrolyte of the all-solid lithium battery comprises (1) Li 2 SP 2 S 5 series; (2) Li 10 GeP 2 S 12 ; (3) PEO (polyethylene oxide) + lithium salt.
  • a 2 g multi-wall carbon tube (Shandong Dazhan Nano Co., Ltd.) was added to 200 ml of deionized water and 20 ml of ethanol, and treated with a 130 W ultrasonic probe for 5 hours to uniformly disperse the carbon tube in the solvent. After that, the sample was added to a spray dryer (Shanghai Yacheng Instrument Equipment Co., Ltd., model YC-015).
  • the setting parameters were: inlet air temperature of 200 ° C, outlet air temperature of 150 ° C, spray pressure of 40 MPa, injection.
  • the amount is 500 mL/h, and the obtained by spray drying is a carbon nanotube microsphere. The above procedure was repeated to prepare carbon nanotube microspheres that were sufficiently used.
  • Lithium iron phosphate positive electrode with a diameter of 15 mm (Suzhou Naxin Energy Technology Co., Ltd., surface density 6.7 mg/cm 2 , lithium iron phosphate content 90%, the same below) is used as the positive electrode of the battery, and the electrolyte is 1 mol/L LiPF 6 EC/DMC/EMC (vol 1/1/1, Dongguan Shanshan Battery Materials Co., Ltd., the same below), the diaphragm is PP diaphragm (Shenzhen Kejing Zhida Technology Co., Ltd. Celgard 2400, the same below).
  • the battery test conditions were 130 cycles of 0.25 C, the voltage range was 4.1 V-2.8 V, and the capacity of the test cell was maintained and the coulombic efficiency.
  • Figure 1 is a graph showing the charge capacity and discharge cycle capacity of the battery for 140 times and the Coulomb efficiency diagram (the first three cycles of the activation electrode in the figure). The battery is still capable of maintaining 70% capacity in 140 cycles and the Coulomb efficiency is maintained at 95% during cycling.
  • the lithium carbon composite preparation process was as described in Example 1.
  • Lithium 15mm lithium cobalt oxide positive electrode (Shenzhen Kejing Zhida Technology Co., Ltd., aluminum foil thickness 15 microns, single-sided active material surface density 128 g / square meter, active substance content 95.7%) as the battery positive electrode
  • the electrolyte is 1mol /L LiPF 6 EC/DMC/EMC (vol 1/1/1)
  • the diaphragm is a PP diaphragm.
  • the battery test conditions were 0.1 C cycle 3 times to activate the battery, 1 C cycle 300 times, charge and discharge voltage range of 4.2-3 V, test cell capacity retention and coulombic efficiency.
  • Fig. 2 is a graph showing the 300-time charge and discharge cycle capacity retention chart and the Coulomb efficiency of the battery. The battery maintains a high coulomb efficiency.
  • the lithium carbon composite preparation process was as described in Example 1.
  • the battery positive electrode 15mm diameter lithium manganate positive electrode (Shenzhen Kejing Zhida Technology Co., Ltd., aluminum foil thickness 15 microns, single-sided active material surface density 166 g / square meter, active material content of 94.2%) as the battery positive electrode, the electrolyte is 1mol /L LiPF 6 EC/DMC/EMC (vol 1/1/1), the diaphragm is a PP diaphragm.
  • the battery test conditions were 0.1 C cycle 3 times to activate the electrode, 1 C cycle 300 times, voltage range 4.5 V-3.3 V, test cell capacity retention and coulombic efficiency.
  • Figure 3 is a capacity retention curve and a Coulomb efficiency curve for the battery. It can be seen that the battery remained stable during 300 cycles and still maintained 88% capacity after 300 cycles.
  • the lithium carbon composite preparation process was as described in Example 1.
  • the active material content was 94.2%.
  • the electrolyte was 1 mol/L LiPF 6 EC/DMC/EMC (vol 1/1/1), and the separator was a PP separator.
  • the battery test conditions were 200 cycles of 0.2 C, the voltage range was 4.2V-3V, and the capacity of the test battery was maintained and the coulombic efficiency.
  • Figure 4 is a capacity retention curve and coulombic efficiency curve for the battery. It can be seen that the coulombic efficiency of the battery is maintained above 95% during the cycle.
  • the lithium carbon composite preparation process was as described in Example 1.
  • the electrolyte is 1 mol/L LiPF 6 EC/DMC/EMC (vol 1/1/ 1)
  • the diaphragm is a PP diaphragm.
  • the battery test conditions were 0.1 C cycle 3 times to activate the battery, 1 C cycle 300 times, voltage range 2.7V-0.8V, test cell capacity retention and Coulomb efficiency.
  • Figure 5 is a capacity retention curve and a Coulomb efficiency curve for the battery. It can be seen that the capacity of the battery during the recycling process is basically maintained, basically maintained at 95%, and the coulombic efficiency can be maintained above 97%.
  • the lithium carbon composite preparation process was as described in Example 1.
  • lithium carbon composite material Approximately 25 mg was dispersed on a foamed copper having a diameter of 15 mm, and pressure was manually applied to firmly press the lithium carbon composite material on the foamed copper as a negative electrode material of the battery.
  • Preparation of positive electrode piece: N-methylpyrrolidone as solvent, lithium titanate (LTO) as positive electrode active material, acetylene black (AB) as conductive agent, polyvinylidene fluoride (PVDF) as binder, mass ratio LTO: AB : PVDF 8:1:1 preparation of slurry, the slurry solid-liquid ratio of 0.2 g: 1 ml, scraped on aluminum foil (scraper thickness 150 microns), dried at 100 ° C, punched into a positive electrode 15 mm in diameter Pole piece, unit area capacity: 1.86mAh/cm 2 (0.2C), as the positive electrode of the battery, the electrolyte is 1mol/L LiTFSI DOL/DME (vol 1/1) with 2% Li
  • Figure 6 is a graph showing the capacity retention and coulombic efficiency of the battery. It can be seen that the capacity of the battery is maintained at 96% during the recycling process, and the coulombic efficiency can be maintained above 97%.
  • lithium carbon composite material lithium acetylene black material
  • acetylene black (Alfa Aesar) was added to 200 ml of deionized water and 20 ml of ethanol, and treated with a 130 W ultrasonic probe for 5 hours to make the acetylene black uniformly dispersed in the solvent.
  • the sample was added to the spray dryer, and the setting parameters were: inlet air temperature of 200 ° C, outlet air temperature of 150 ° C, spray pressure of 40 MPa, injection volume of 500 mL / h, spray drying to obtain sprayed acetylene Black (particle size 70-80 nm). The above procedure was repeated to prepare a spray of acetylene black which was sufficiently used.
  • lithium acetylene black composite Approximately 20 mg was dispersed on foamed copper having a diameter of 15 mm, and pressure was manually applied to firmly press the lithium carbon composite on the copper foam as a negative electrode material of the battery.
  • a lithium iron phosphate positive electrode sheet having a diameter of 15 mm was used as a positive electrode of the battery, and the electrolyte was 1 mol/L LiPF 6 EC/DMC/EMC (vol1/1/1), and the separator was a PP separator.
  • the battery test conditions were 0.1 C cycle 4 times to activate the electrode, 1 C cycle 300 times, voltage ranged from 4.1 V to 2.5 V, test cell capacity retention and coulombic efficiency.
  • Figure 7 shows the battery capacity retention curve and the Coulomb efficiency curve. It can be seen that after 300 cycles, the battery capacity can still be maintained at 80%, and the cycle efficiency is maintained above 98%.
  • the lithium carbon composite preparation process was as described in Example 1.
  • p-xylene 20 mg: 20 mg: 40 mg: 320 mg: 1.5 ml
  • styrene-butadiene rubber (Sigma-Aldrich China, molecular weight 2 million, the same below) and polystyrene (Sigma-Aldrich China, melt index can be 6g/min (200 ° C / 5kg), the same below) as binder
  • acetylene Black is a conductive agent
  • p-xylene water content ⁇ 50ppm, Shanghai Aladdin Biochemical Technology Co., Ltd., the same below
  • the uniformly stirred slurry was coated on a copper foil having a blade thickness of 250 ⁇ m and a copper foil thickness of 10 ⁇ m.
  • the above procedure was carried out in an argon-filled glove box (moisture content ⁇ 10 ppm, oxygen ⁇ 10 ppm).
  • a lithium iron phosphate positive electrode sheet having a diameter of 15 mm was used as a positive electrode of the battery, and the electrolyte was 1 mol/L LiPF 6 EC/DMC/EMC (vol1/1/1), and the separator was a PP separator.
  • the battery test conditions were 90 cycles of 0.5C, the voltage range was 4.1V-2.5V, and the capacity of the test battery was maintained and the coulombic efficiency.
  • Figure 8 is the battery capacity retention curve and the Coulomb efficiency curve. After 90 cycles, the battery is still able to maintain a capacity of more than 70%.
  • a 2 g multi-wall carbon tube (Shandong Dazhan Nano Co., Ltd.) was added to 200 ml of deionized water and 20 ml of ethanol, and treated with a 130 W ultrasonic probe for 5 hours to uniformly disperse the carbon tube in the solvent. After that, the sample was added to a spray dryer (Shanghai Yacheng Instrument Equipment Co., Ltd., model YC-015).
  • the setting parameters were: inlet air temperature of 200 ° C, outlet air temperature of 150 ° C, spray pressure of 40 MPa, injection.
  • the amount is 500 mL/h, and the obtained by spray drying is a carbon nanotube microsphere. The above procedure was repeated to prepare carbon nanotube microspheres that were sufficiently used.
  • styrene-butadiene rubber and polystyrene are binders
  • acetylene black is a conductive agent
  • p-xylene is a solvent.
  • the uniformly stirred slurry was coated on a copper foil having a blade thickness of 250 ⁇ m and a copper foil thickness of 10 ⁇ m.
  • the pole piece was dried overnight at 60 ° C vacuum (-0.1 Mpa), and then the dried pole piece was punched into a disk having a diameter of 15 ⁇ m as a negative electrode piece of the battery.
  • the above procedure was carried out in an argon-filled glove box (moisture content ⁇ 10 ppm, oxygen ⁇ 10 ppm).
  • a lithium iron phosphate positive electrode sheet having a diameter of 15 mm was used as a positive electrode of the battery, and the electrolyte was 1 mol/L LiPF 6 EC/DMC/EMC (vol1/1/1), and the separator was a PP separator.
  • the battery test conditions were 90 cycles of 0.5C, the voltage range was 4.1V-2.5V, and the capacity of the test battery was maintained and the coulombic efficiency.
  • Figure 9 is the battery capacity retention curve and coulombic efficiency curve. After 200 cycles, the battery capacity can still be maintained above 60%.
  • Carbon nanotube microspheres were prepared as described in Example 8.
  • styrene-butadiene rubber and polystyrene are binders
  • acetylene black is a conductive agent
  • p-xylene is a solvent.
  • the uniformly stirred slurry was coated on a copper foil having a blade thickness of 250 ⁇ m and a copper foil thickness of 10 ⁇ m.
  • the pole piece was dried overnight at 60 ° C vacuum (-0.1 Mpa), and then the dried pole piece was punched into a disk having a diameter of 15 ⁇ m as a negative electrode piece of the battery.
  • the above procedure was carried out in an argon-filled glove box (moisture content ⁇ 10 ppm, oxygen ⁇ 10 ppm).
  • a lithium iron phosphate positive electrode sheet having a diameter of 15 mm was used as a positive electrode of the battery, and the electrolyte was 1 mol/L LiPF 6 EC/DMC/EMC (vol1/1/1), and the separator was a PP separator.
  • the battery test conditions were 90 cycles of 0.5C, the voltage range was 4.1V-2.5V, and the capacity of the test battery was maintained and the coulombic efficiency.
  • Figure 10 is the battery capacity retention curve and the Coulomb efficiency curve. It can be seen that the battery capacity can still be maintained above 90% after 90 cycles. The coulombic efficiency of the battery is maintained above 95%, and the capacity of the battery after 200 cycles. Can still maintain more than 60%.
  • a 2 g multi-wall carbon tube (Shandong Dazhan Nano Co., Ltd.) was added to 200 ml of deionized water and 20 ml of ethanol, and treated with a 130 W ultrasonic probe for 5 hours to uniformly disperse the carbon tube in the solvent. After that, the sample was added to a spray dryer (Shanghai Yacheng Instrument Equipment Co., Ltd., model YC-015).
  • the setting parameters were: inlet air temperature of 200 ° C, outlet air temperature of 150 ° C, spray pressure of 40 MPa, injection.
  • the amount is 500 mL/h, and the obtained by spray drying is a carbon nanotube microsphere. The above procedure was repeated to prepare carbon nanotube microspheres that were sufficiently used.
  • the sulfur-carbon positive electrode tab is punched into a 15 mm diameter disc as the positive electrode of the battery, and the electrolyte is 1 mol/L LiTFSI DOL/DME (vol 1/1/1, LiTFSI: bistrifluoromethylsulfonimide lithium or Lithium bis(trifluoromethanesulfonate)imide, DOL: 1,3-dioxolane, DME: ethylene glycol dimethyl ether, the same as below, Dongguan Shanshan Battery Materials Co., Ltd.), the separator is a PP separator ( Shenzhen Kejing Zhida Technology Co., Ltd. Celgard 2400, the same below).
  • the test condition is 0.25C constant current charge and discharge, and the charge and discharge voltage range is: 1.5V-2.8V.
  • Figure 11 is a capacity retention curve of the battery. It can be seen that the negative electrode material can be used for a lithium sulfur battery, and its capacity can be maintained at 80% or more of the initial capacity after 20 cycles.
  • the lithium carbon composite material and the negative electrode tab were prepared in the same manner as in Example 11.
  • PAN molecular weight: 150,000, Belling Technology Co., Ltd.
  • the diaphragm is a PP diaphragm.
  • the test condition is 0.25C constant current charge and discharge, and the charge and discharge voltage range is: 1.5V-2.8V.
  • Figure 12 is a capacity retention curve of the battery. After 50 cycles, the battery capacity was maintained at 95%.
  • a 2 g multi-wall carbon tube (Shandong Dazhan Nano Co., Ltd.) was added to 200 ml of deionized water and 20 ml of ethanol, and treated with a 130 W ultrasonic probe for 5 hours to uniformly disperse the carbon tube in the solvent. After that, the sample was added to a spray dryer (Shanghai Yacheng Instrument Equipment Co., Ltd., model YC-015).
  • the setting parameters were: inlet air temperature of 200 ° C, outlet air temperature of 150 ° C, spray pressure of 40 MPa, injection.
  • the amount is 500 mL/h, and the obtained by spray drying is a carbon nanotube microsphere. The above procedure was repeated to prepare carbon nanotube microspheres that were sufficiently used.
  • styrene-butadiene rubber (Sigma-Aldrich China, molecular weight 2 million, the same below) and polystyrene (Sigma-Aldrich China, melt index can be 6g/min (200 ° C / 5kg), the same below) as binder
  • acetylene Black is a conductive agent
  • p-xylene water content ⁇ 50ppm, Shanghai Aladdin Biochemical Technology Co., Ltd., the same below
  • the pole piece was dried overnight at 60 ° C vacuum (-0.1 Mpa), and then the dried pole piece was punched into a disk having a diameter of 15 ⁇ m as a negative electrode piece of the battery.
  • the above procedure was carried out in an argon-filled glove box (moisture content ⁇ 10 ppm, oxygen ⁇ 10 ppm).
  • the electrolyte was 1 mol/L LiTFSI DOL/DME, and the separator was a PP separator.
  • the test condition is 0.25C constant current charge and discharge, and the charge and discharge voltage range is: 1.5V-2.8V.
  • Figure 13 is a capacity retention curve of the battery. After 40 cycles, the battery capacity can still be maintained at around 80, showing better capacity retention performance.
  • the preparation method of the carbon nanotube microspheres is as described in Example 11.
  • the preparation method of the negative electrode tab is as shown in Example 13.
  • the preparation method of the positive electrode tab was as shown in Example 13.
  • Figure 14 is a graph showing the capacity retention of the battery. The battery is still capable of maintaining 75% capacity after 40 cycles.
  • the preparation method of the lithium-silicon alloy-containing carbon composite material is as described in Example 13.
  • the PAN/S positive electrode tab preparation method is as described in Example 12.
  • the blade thickness used therein was 300 ⁇ m, and the sulfur content per unit area of the pole piece after drying was 2.3 mg/cm 2 .
  • Figure 15 is a capacity retention curve of the battery. After 100 cycles, the battery can still maintain more than 95% capacity.
  • the preparation method of the lithium-magnesium alloy containing carbon composite material is as described in Example 14.
  • the PAN/S positive electrode tab preparation method was as described in Example 12.
  • the blade thickness used therein was 300 ⁇ m, and the sulfur content per unit area of the pole piece after drying was 2.3 mg/cm 2 .
  • Figure 16 is a capacity retention curve of the battery. After 100 cycles, the battery can still maintain more than 95% capacity.
  • a 2 g multi-wall carbon tube (Shandong Dazhan Nano Co., Ltd.) was added to 200 ml of deionized water and 20 ml of ethanol, and treated with a 130 W ultrasonic probe for 5 hours to uniformly disperse the carbon tube in the solvent. After that, the sample was added to a spray dryer (Shanghai Yacheng Instrument Equipment Co., Ltd., model YC-015).
  • the setting parameters were: inlet air temperature of 200 ° C, outlet air temperature of 150 ° C, spray pressure of 40 MPa, injection.
  • the amount is 500 mL/h, and the obtained by spray drying is a carbon nanotube microsphere.
  • the button battery case is a modified CR2032 battery case in which a hole is punched in the battery positive case so that oxygen can enter the battery system (the same below).
  • the electrolyte is 1M LiPF6EC/DMC/EMC (vol 1/1/1, EC: ethylene carbonate, DMC: dimethyl carbonate, EMC: ethyl methyl carbonate, Dongguan Shanshan Battery Materials Co., Ltd., the same below), diaphragm For the glass fiber membrane (Whatman, the same below), the battery was placed in an oxygen atmosphere.
  • Fig. 17 is a graph showing the charge and discharge curves of the simulated battery. It can be seen that the battery composed of the lithium negative electrode and the positive electrode prepared by the above method can work normally with the lithium carbon composite material as the negative electrode material.
  • Fig. 18 is a graph showing the capacity retention of the button battery, and it can be seen that the lithium oxygen battery can be cycled 6 times.
  • a 2 g multi-wall carbon tube (Shandong Dazhan Nano Co., Ltd.) was added to 200 ml of deionized water and 20 ml of ethanol, and treated with a 130 W ultrasonic probe for 5 hours to uniformly disperse the carbon tube in the solvent. After that, the sample was added to a spray dryer (Shanghai Yacheng Instrument Equipment Co., Ltd., model YC-015).
  • the setting parameters were: inlet air temperature of 200 ° C, outlet air temperature of 150 ° C, spray pressure of 40 MPa, injection.
  • the amount is 500 mL/h, and the obtained by spray drying is a carbon nanotube microsphere. The above procedure was repeated to prepare carbon nanotube microspheres that were sufficiently used.
  • styrene-butadiene rubber (Sigma-Aldrich China, molecular weight 2 million, the same below) and polystyrene (Sigma-Aldrich China, melt index can be 6g/min (200 ° C / 5kg), the same below) as binder
  • acetylene Black is a conductive agent
  • p-xylene water content ⁇ 50ppm, Shanghai Aladdin Biochemical Technology Co., Ltd., the same below
  • the uniformly stirred slurry was coated on a copper foil having a blade thickness of 250 ⁇ m and a copper foil thickness of 10 ⁇ m. Dry at 60 ° C overnight (greater than 10 hours, -0.1 MPa).
  • the dried pole piece was punched into a disk having a diameter of 15 mm as a negative electrode of a lithium-oxygen battery.
  • the above procedure was carried out in an argon-filled glove box (moisture content ⁇ 10 ppm, oxygen ⁇ 10 ppm).
  • FIG. 19 is a charge-discharge curve of the first and sixth cycles of a lithium-oxygen battery.
  • the lithium-silicon alloy-carbon composite is used as an active material, and a negative electrode sheet is prepared by a coating method, so that the lithium-oxygen battery can be operated, and The battery has a high capacity.
  • Figure 20 is a capacity retention curve of the lithium oxygen battery, as can be seen from the graph, the battery can be maintained for 5 cycles.
  • a 2 g multi-wall carbon tube (Shandong Dazhan Nano Co., Ltd.) was added to 200 ml of deionized water and 20 ml of ethanol, and treated with a 130 W ultrasonic probe for 5 hours to uniformly disperse the carbon tube in the solvent.
  • the sample was added to a spray dryer (Shanghai Yacheng Instrument Equipment Co., Ltd., model YC-015), and the setting parameters were: inlet air temperature of 200 ° C, outlet air temperature of 150 ° C, spray The pressure is 40 MPa, the injection volume is 500 mL/h, and the spray drying results in carbon nanotube microspheres. The above procedure was repeated to prepare carbon nanotube microspheres that were sufficiently used.
  • styrene-butadiene rubber and polystyrene are binders
  • acetylene black is a conductive agent
  • p-xylene is a solvent.
  • the uniformly stirred slurry was coated on a copper foil having a blade thickness of 250 ⁇ m and a copper foil thickness of 10 ⁇ m.
  • the dried pole piece was punched into a disk having a diameter of 15 mm as a negative electrode of a lithium-oxygen battery.
  • the above procedure was carried out in an argon-filled glove box (moisture content ⁇ 10 ppm, oxygen ⁇ 10 ppm).
  • Figure 21 is a graph showing the charge and discharge curves of the first and seventh cycles of the lithium-oxygen battery.
  • the above-mentioned materials and methods were used to prepare the negative electrode tab, which enabled the lithium-oxygen battery to operate. And the battery has a high capacity.
  • Fig. 22 is a capacity retention curve of the lithium oxygen battery, as can be seen from the graph, the battery can be maintained for 7 cycles.
  • a 2 g multi-wall carbon tube (Shandong Dazhan Nano Co., Ltd.) was added to 200 ml of deionized water and 20 ml of ethanol, and treated with a 130 W ultrasonic probe for 5 hours to uniformly disperse the carbon tube in the solvent. After that, the sample was added to a spray dryer (Shanghai Yacheng Instrument Equipment Co., Ltd., model YC-015).
  • the setting parameters were: inlet air temperature of 200 ° C, outlet air temperature of 150 ° C, spray pressure of 40 MPa, injection.
  • the amount is 500 mL/h, and the obtained by spray drying is a carbon nanotube microsphere.
  • lithium carbon composite material Approximately 25 milligrams of lithium carbon composite material was dispersed on foamed copper having a diameter of 15 mm, and pressure was manually applied to firmly press the lithium carbon composite material on foamed copper (Suzhou Taili Foam Metal Factory, thickness 1.6 mm).
  • the pressure is 20-30KPa, which is directly used as the negative electrode of the battery (button battery 2025, Shenzhen Biyuan Battery Co., Ltd., the same below).
  • iron sulfide Shieldzhen Yunan Energy Technology Co., Ltd.
  • acetylene black Alfa Aesar
  • LA132 water-based binder, Chengdu Yindi Le Power Technology Co., Ltd.
  • stirring time > 10 hours Take the corresponding substance, add 750mg of water, magnetic stirring, stirring speed 400-600r / min, stirring time > 10 hours.
  • the slurry was knife coated onto an aluminum foil with a doctor blade thickness of 150 microns and then dried overnight at 80 degrees Celsius (greater than 10 hours).
  • the dried iron sulfide pole piece has a mass of 5.5 milligrams per unit square centimeter of iron sulfide. It is punched into a 15 mm diameter positive electrode piece, and the above negative electrode piece is composed of a battery, and the electrolyte is 1 mol/L LiTFSI DOL/DME (vol 1/1) (LiTFSI: lithium bistrifluoromethylsulfonimide or two (Trifluoromethanesulfonic acid) lithium imide, DOL: 1,3-dioxolane, DME: ethylene glycol dimethyl ether, Dongguan Shanshan Battery Materials Co., Ltd., the same below), the diaphragm is PP diaphragm (Shenzhen Kejing Zhida Technology Co., Ltd., Celgard 2400, the same below).
  • the battery test conditions were 0.1 C constant current discharge to 1 V.
  • Figure 23 is a graph showing the specific capacity voltage of a constant current discharge. It can be seen that the lithium carbon composite material is used as the negative electrode active material, and the negative electrode sheet prepared by the above method can be applied to an iron sulfide primary battery.
  • the preparation method of the lithium carbon composite material and the negative electrode tab is as shown in Example 20.
  • the battery adopts CR2025 button battery
  • the electrolyte is 1M LiClO 4 PC (LiClO 4 lithium perchlorate, PC propylene carbonate, Suzhou Ganmin Chemical Reagent Co., Ltd.)
  • the diaphragm is PP diaphragm
  • the charge and discharge voltage is 3.8–1.5V.
  • the constant current charge and discharge current is 50 mA/g.
  • Fig. 24 is a capacity retention curve of the battery, which has a high initial capacity and can maintain a capacity of 20% after 15 cycles.
  • the preparation method of the carbon nanotube microspheres is as described in Example 20.
  • styrene-butadiene rubber (Sigma-Aldrich China, molecular weight 2 million) and polystyrene (Sigma-Aldrich China, melt index can be 6g/min (200 ° C/5kg)) as binder, acetylene black as conductive agent, Xylene (water content ⁇ 50ppm, Shanghai Aladdin Biochemical Technology Co., Ltd., the same below) as a solvent.
  • the uniformly stirred slurry was coated on a copper foil having a blade thickness of 250 ⁇ m and a copper foil thickness of 10 ⁇ m.
  • the pole piece was dried overnight at 60 ° C vacuum (-0.1 Mpa), and then the dried pole piece was punched into a disk having a diameter of 15 ⁇ m as a negative electrode piece of the battery.
  • the above procedure was carried out in an argon-filled glove box (moisture content ⁇ 10 ppm, oxygen ⁇ 10 ppm).
  • the preparation method of the iron sulfide positive electrode tab is as described in Example 20.
  • the battery assembly and test methods are as described in Example 20.
  • Fig. 25 is a discharge curve of the battery, and the negative electrode material prepared by the above materials and methods can be matched with the iron sulfide positive electrode to constitute a primary battery.
  • the preparation method of the carbon nanotube microspheres is as described in Example 20.
  • the preparation method of the iron sulfide positive electrode tab is as described in Example 20.
  • the battery assembly and test methods are as described in Example 20.
  • Figure 26 is the discharge curve of the battery.
  • the negative electrode prepared by the above materials and methods can be applied to an iron sulfide battery.
  • the preparation method of the carbon nanotube microspheres is as described in Example 20.
  • the lithium-containing silicon alloy carbon composite negative electrode tab preparation method is as described in Example 22.
  • the preparation method of the manganese dioxide positive electrode tab is as described in Example 21.
  • Figure 27 is a capacity retention curve of the battery, which is capable of maintaining a capacity of more than 75% after 50 cycles.
  • the preparation method of the carbon nanotube microspheres is as described in Example 20.
  • the lithium-containing magnesium alloy carbon composite negative electrode tab preparation method is as described in Example 23.
  • the preparation method of the manganese dioxide positive electrode tab is as described in Example 21.
  • Figure 28 is a capacity retention curve of the battery. After 50 cycles, the battery can maintain a capacity of 70% or more.
  • Preparation of lithium carbon composite material 2g multi-wall carbon tube (Shandong Dazhan Nano Co., Ltd.) was added to 200 ml of deionized water and 20 ml of ethanol, and treated with a 130 W ultrasonic probe for 5 hours, so that the carbon tube was uniformly dispersed in the solvent. After that, the sample was added to a spray dryer (Shanghai Yacheng Instrument Equipment Co., Ltd., model YC-015). The setting parameters were: inlet air temperature of 200 ° C, outlet air temperature of 150 ° C, spray pressure of 40 MPa, injection. The amount is 500 mL/h, and the obtained by spray drying is a carbon nanotube microsphere. The above procedure was repeated to prepare carbon nanotube microspheres that were sufficiently used.
  • Preparation of the negative electrode Disperse about 20 mg of lithium carbon composite material on the foamed copper with a diameter of 15 mm, and manually apply pressure so that the lithium carbon composite material is firmly pressed on the copper foam and directly used as a battery (button battery, CR2025 type, Shenzhen Biyuan Electronics Co., Ltd., the same as the negative pole piece.
  • Preparation of solid electrolyte The raw material is placed in a ball mill tank in a stoichiometric ratio (molar ratio) of 80Li 2 S (Belling Technology, the same below): 20P 2 S 5 (Nanjing reagent, the same below), and mixed at 500 rpm. After ball milling for 15 hours, a LPOS amorphous precursor was obtained, and then the precursor was placed in a muffle furnace at 250 ° C for 4 hours to obtain a solid electrolyte having a main phase of Li 3 PS 4 .
  • Positive active material NCA nickel-cobalt-aluminum ternary material, Shenzhen Beite Rui New Energy Materials Co., Ltd.
  • Activated carbon Shenzhen Kejing Zhida Technology Co., Ltd., the same below
  • PVDF polyvinylidene fluoride, Zhejiang Funolin Chemical New Material Co., Ltd.
  • ratio mass ratio
  • Battery assembly assembled in the order of positive electrode, solid electrolyte, and negative electrode.
  • the test voltage range is 2.8-4.2V.
  • the cycle curve of 0.1C at 25°C is shown in Figure 29.
  • the specific capacity value after 20 cycles is 89 mAh/g, which is 77.4% of the initial capacity.
  • the lithium carbon composite material was prepared in the same manner as in Example 26.
  • styrene-butadiene rubber (Sigma-Aldrich China, molecular weight 2 million, the same below) and polystyrene (Sigma-Aldrich China, melt index can be 6g/min (200 ° C / 5kg), the same below) as binder
  • acetylene Black is a conductive agent
  • p-xylene water content ⁇ 50ppm, Shanghai Aladdin Biochemical Technology Co., Ltd., the same below
  • the uniformly stirred slurry was coated on a copper foil having a blade thickness of 200 ⁇ m and a copper foil thickness of 8 ⁇ m.
  • the pole piece was dried overnight at 60 ° C vacuum (-0.1 Mpa), and then the dried pole piece was punched into a disk having a diameter of 15 ⁇ m as a negative electrode piece of the battery.
  • the above procedure was carried out in an argon-filled glove box (moisture content ⁇ 10 ppm, oxygen ⁇ 10 ppm).
  • Solid electrolyte preparation in a argon glove box, a ball mill was mixed in a molar ratio of 5:1:1 in a Li 2 S:P 2 S 5 :GeS 2 (Beijing Thompson Biotech Co., Ltd.), high-energy ball mill at 500 rpm After 5 hours, the ball abrasive was taken out, pressed into a round cake with a density of 2.5 g/cm 3 by a pressure device, and the round ball abrasive was placed in a crucible, and the temperature was 550 ° C in a tube furnace (pure argon atmosphere). After calcination for 6 hours, to be naturally cooled, a Li 10 GeP 2 S 12 solid electrolyte was prepared.
  • NCM nickel-cobalt-manganese ternary material, Ningbo Jinhe New Material Co., Ltd.
  • acetylene black Ada Aisha Tianjin Chemical Co., Ltd.
  • PVDF polyvinylidene fluoride, Zhejiang Funolin
  • Battery assembly assembled into a battery test in the order of positive electrode, solid electrolyte, and negative electrode.
  • the solid state battery is thermostated at 120 ° C for 2 hours in a pure argon atmosphere, and then tested for electrochemical performance.
  • the voltage range is 3.0-4.2V at 25
  • the cycle curve of 0.1 C at ° C is shown in Fig. 30, and the specific capacity value after the 20 cycles is 91 mAh/g, which is 72.8% of the initial capacity.
  • the carbon nanotube microspheres were prepared as in Example 26.
  • styrene-butadiene rubber (Sigma-Aldrich China, molecular weight 2 million, the same below) and polystyrene (Sigma-Aldrich China, melt index can be 6g/min (200 ° C / 5kg), the same below) as binder
  • acetylene Black is a conductive agent
  • p-xylene water content ⁇ 50ppm, Shanghai Aladdin Biochemical Technology Co., Ltd., the same below
  • the pole piece was dried overnight at 60 ° C vacuum (-0.1 Mpa), and then the dried pole piece was punched into a disk having a diameter of 15 ⁇ m as a negative electrode piece of the battery.
  • the above procedure was carried out in an argon-filled glove box (moisture content ⁇ 10 ppm, oxygen ⁇ 10 ppm).
  • PEO polyethylene oxide
  • LiClO 4 Hubei Baijierui New Material Co., Ltd.
  • titanium dioxide Belling Technology
  • a certain amount of titanium dioxide powder was added to the above PEO solution, magnetically stirred for 5 hours, and ultrasonically dispersed for 1 hour to obtain a mucus of the composite electrolyte.
  • the mucus of the electrolyte was transferred to a mold of polytetrafluoroethylene, the solvent was volatilized and naturally formed into a film, and then vacuum-dried at 50 ° C for 24 hours to completely evaporate the solvent, thereby obtaining a composite polymer electrolyte membrane to be used.
  • Battery assembly assembled in the order of positive electrode, polymer electrolyte membrane, and negative electrode.
  • the test voltage range is 2-4V.
  • the cycle curve of 0.1C at 25 °C is shown in Figure 31.
  • the specific capacity value after 20 cycles is shown. 134 mAh/g, which is 76.6% of the initial capacity.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne une électrode contenant du lithium, son procédé de préparation et une batterie au lithium contenant l'électrode. L'électrode contenant du lithium comprend un collecteur de courant et une couche de matériau d'électrode comprenant un matériau composite de lithium-carbone en tant que matériau actif collé sur la surface du collecteur de courant, la couche de matériau d'électrode est constituée d'un matériau composite de carbone à squelette de lithium métal à l'échelle micro et nanométrique, ou la couche de matériau d'électrode contient un matériau composite de carbone à squelette d'alliage de lithium à l'échelle micro et nanométrique. L'électrode contenant du lithium peut inhiber la croissance de dendrites de lithium.
PCT/CN2017/105654 2017-07-26 2017-10-11 Électrode contenant du lithium, son procédé de préparation et batterie au lithium la comprenant WO2019019407A1 (fr)

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
CN201710617871.1A CN109309205A (zh) 2017-07-26 2017-07-26 锂硫电池负极、其制备方法和锂硫电池
CN201710617327.7 2017-07-26
CN201710618561.1 2017-07-26
CN201710617871.1 2017-07-26
CN201710618561.1A CN109309195A (zh) 2017-07-26 2017-07-26 含锂电极、其制备方法和含有该电极的锂离子电池
CN201710618423.3A CN109309206A (zh) 2017-07-26 2017-07-26 一次锂电池、二次锂电池及其制备方法
CN201710617327.7A CN109309202A (zh) 2017-07-26 2017-07-26 锂氧电池负极、其制备方法和锂氧电池
CN201710618423.3 2017-07-26
CN201710684880.2 2017-08-11
CN201710684880.2A CN109390556A (zh) 2017-08-11 2017-08-11 全固态锂电池负极、其制备方法和全固态锂电池

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Publication number Priority date Publication date Assignee Title
CN1487617A (zh) * 2003-07-30 2004-04-07 ��������ǿ��Դ�Ƽ����޹�˾ 大容量聚合物锂离子电池及其制造方法
CN1597502A (zh) * 2004-09-13 2005-03-23 东北师范大学 纳米碳与石墨碳混合材料及其在锂离子电池中的应用
CN102593446A (zh) * 2012-02-22 2012-07-18 清华大学 一种锂离子电池活性电极材料的制备方法
US20150295246A1 (en) * 2013-09-11 2015-10-15 Lg Chem, Ltd. Lithium electrode and lithium secondary battery comprising the same
CN105374991A (zh) * 2014-08-13 2016-03-02 中国科学院苏州纳米技术与纳米仿生研究所 金属锂-骨架碳复合材料及其制备方法、负极和二次电池
CN106684342A (zh) * 2015-11-11 2017-05-17 中国科学院苏州纳米技术与纳米仿生研究所 硅-碳纳米管微球、其金属锂复合物与其制备方法及应用

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1487617A (zh) * 2003-07-30 2004-04-07 ��������ǿ��Դ�Ƽ����޹�˾ 大容量聚合物锂离子电池及其制造方法
CN1597502A (zh) * 2004-09-13 2005-03-23 东北师范大学 纳米碳与石墨碳混合材料及其在锂离子电池中的应用
CN102593446A (zh) * 2012-02-22 2012-07-18 清华大学 一种锂离子电池活性电极材料的制备方法
US20150295246A1 (en) * 2013-09-11 2015-10-15 Lg Chem, Ltd. Lithium electrode and lithium secondary battery comprising the same
CN105374991A (zh) * 2014-08-13 2016-03-02 中国科学院苏州纳米技术与纳米仿生研究所 金属锂-骨架碳复合材料及其制备方法、负极和二次电池
CN106684342A (zh) * 2015-11-11 2017-05-17 中国科学院苏州纳米技术与纳米仿生研究所 硅-碳纳米管微球、其金属锂复合物与其制备方法及应用

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