WO2017117838A1 - 一种低温无机熔盐铝离子超级电容电池及其制备方法 - Google Patents

一种低温无机熔盐铝离子超级电容电池及其制备方法 Download PDF

Info

Publication number
WO2017117838A1
WO2017117838A1 PCT/CN2016/072872 CN2016072872W WO2017117838A1 WO 2017117838 A1 WO2017117838 A1 WO 2017117838A1 CN 2016072872 W CN2016072872 W CN 2016072872W WO 2017117838 A1 WO2017117838 A1 WO 2017117838A1
Authority
WO
WIPO (PCT)
Prior art keywords
aluminum
positive electrode
molten salt
sulfide
electrolyte
Prior art date
Application number
PCT/CN2016/072872
Other languages
English (en)
French (fr)
Inventor
焦树强
宋阳
王俊香
李海滨
Original Assignee
北京金吕能源科技有限公司
甘肃鑫吕能源材料有限公司
北京科技大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 北京金吕能源科技有限公司, 甘肃鑫吕能源材料有限公司, 北京科技大学 filed Critical 北京金吕能源科技有限公司
Publication of WO2017117838A1 publication Critical patent/WO2017117838A1/zh

Links

Images

Classifications

    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/56—Solid electrolytes, e.g. gels; Additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • 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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
    • 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
    • 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
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the invention belongs to the field of a novel green energy battery used in the electronics industry, the communication industry and the electric vehicle power battery, and particularly relates to a low-temperature inorganic molten salt aluminum ion super capacitor battery and a preparation method thereof.
  • lithium-ion batteries have been seeking new battery systems due to the safety hazards of the formation of dendritic crystals.
  • low-temperature molten salt secondary batteries have entered people's sight. Compared with the normal temperature ion battery, the low temperature molten salt secondary battery has a high ion mobility, a small electrode polarization, and is advantageous for energy efficient storage and conversion.
  • the invention adopts graphite with broad raw materials and low cost, transition metal sulfide and metal aluminum as positive and negative electrodes of the battery, and uses molten halide containing aluminum ions as electrolyte, which can be effectively and widely applied to storage of various renewable clean energy sources. Used.
  • the invention provides a molten salt battery which can be used for energy storage and conversion of renewable energy such as wind energy, solar energy and tidal energy, and has outstanding charge and discharge specific capacity, excellent cycle performance, energy conversion efficiency and good safety.
  • the low-temperature inorganic molten salt aluminum ion supercapacitor battery and the preparation method thereof can be applied to the high-efficiency storage and conversion of various green clean energy sources on a large scale.
  • a low temperature inorganic molten salt aluminum ion supercapacitor battery comprising a positive electrode, a negative electrode, and an electrolyte and an electrolytic cell device, wherein the positive electrode is a carbon material and a transition metal sulfide
  • the positive electrode is a carbon material and a transition metal sulfide
  • the negative electrode is a solid metal aluminum or a solid alloy thereof
  • the electrolyte is a mixed molten salt system of aluminum chloride and an alkali metal or alkaline earth metal chloride.
  • the ratio of each component of the electrolyte is: the molar concentration ratio of the aluminum trichloride to the alkali metal chloride or the alkaline earth metal chloride is: 1-4:1; the additive is added in an amount not exceeding three And the alkali metal comprises LiCl, NaCl, KCl, RbCl or CsCl; the alkaline earth metal chloride comprises MgCl 2 , CaCl 2 or BaCl 2 ; The additive comprises LiAlBr 4 , NaAlBr 4 , KAlBr 4 , LiAlCl 4 , NaAlCl 4 or KAlCl 4 :1.
  • the ratio of each component of the positive electrode is: 10% to 50% by mass of the carbon material, and 50% to 90% by mass of the transition metal sulfide;
  • the carbon material includes: graphite, carbon paper, Carbon Fiber paper, carbon nanotubes, graphene, expanded graphite or carbon black;
  • the transition metal sulfides include: nickel sulfide, titanium sulfide, copper sulfide, iron sulfide, lead sulfide, zirconium sulfide, vanadium sulfide, chromium sulfide, cobalt sulfide Or molybdenum sulfide.
  • the positive electrode or the solid negative electrode has a shape of a sheet, a rectangular parallelepiped, a cube, a cylindrical block or other irregular block having at least one plane.
  • the negative electrode is a binary or multi-component alloy formed of solid metal aluminum or solid metal aluminum and metal gallium, copper, chromium, iron, nickel, lead, antimony, tin or silver.
  • the operating temperature of the capacitor battery is 50-300 °C.
  • Another object of the present invention is to provide a method for preparing the above low temperature inorganic molten salt aluminum ion supercapacitor battery, which comprises the following steps:
  • Step 1 Prepare the positive electrode: mix the carbon material and the transition metal sulfide according to the design ratio, and then wrap it with the separator material, and then connect with the positive high temperature conductive rod with the thread, clamp, hook, inlay or high temperature resistant wire as the positive electrode. ,spare;
  • Step 2 Prepare the negative electrode: the solid aluminum or aluminum alloy is connected with the negative conductive rod as a negative electrode by means of threading, clamping, hooking, inlay or high temperature resistant wire;
  • Step 3 Prepare a molten salt electrolyte system: the aluminum trichloride and the alkali metal chloride or the alkaline earth metal chloride are weighed according to a molar concentration ratio of 1 to 4:1, uniformly mixed, and then added with a certain amount of additives to obtain a molten salt electrolyte system, wherein the additive is added in an amount not exceeding 20% of the total mass of the aluminum trichloride and the alkali metal chloride or alkaline earth metal chloride;
  • Step 4 Assembling: The molten salt electrolyte system prepared in the step 3 is added to the reaction vessel to a thickness of 100-5000 mm, and then the preparation step 1 is performed to obtain a positive electrode and the second step is prepared to obtain a negative electrode, followed by heating to 50-300 ° C. Finally, by adjusting the position of the positive electrode block to adjust the position of the positive electrode block, soaking it in the electrolyte for a certain time, the inorganic molten salt aluminum ion secondary supercapacitor battery is obtained.
  • the negative-temperature resistant high-temperature conductive rod is made of a metal or an alloy including stainless steel, molybdenum, titanium, nickel, or the like including but not limited to them.
  • the aluminum trichloride, alkali metal chloride or alkaline earth metal chloride is ground into particles having a particle diameter of 0.001 to 50 mm in an oxygen-free and anhydrous environment.
  • the molten salt electrolyte system may have a thickness of 1000-2000 mm.
  • the invention has the beneficial effects that: according to the above technical solution, the invention uses a composite of a carbon material and a transition metal sulfide as a positive electrode, a solid metal aluminum or an alloy as a negative electrode, a mixture of aluminum chloride and an alkali metal or alkaline earth metal chloride.
  • the molten salt system constitutes a molten salt aluminum ion secondary supercapacitor battery. It has the following characteristics: AlCl 3 is used as a component of the electrolyte molten salt system, and the mass percentage of aluminum ions in the electrolyte molten salt system is 60%-78.2%.
  • the aluminum content of the negative electrode in the earth's crust is abundant and the price is cheap, which greatly reduces the preparation cost of the battery.
  • the carbon material and the transition metal sulfide have a layered structure, which facilitates the embedding and extraction of the aluminum element, and has excellent chemical stability and thermal stability. Cyclic stability, charge-discharge specific capacity and cycle efficiency of secondary aluminum ion molten salt battery; molten salt as electrolyte, high conductivity, good thermal stability, high ion mobility and wide potential window, The internal resistance of the secondary aluminum ion molten salt battery of the invention is effectively reduced, thereby improving the energy conversion efficiency. Based on the above characteristics, the secondary aluminum ion molten salt battery of the invention can be safely and reliably, clean and environmentally friendly, and can be widely used for energy storage and conversion of renewable energy such as wind energy, solar energy and tidal energy.
  • Figure 1 shows that the electrolyte is a supporting electrolyte with NaCl:AlCl 3 in a molar ratio of 1:1.5.
  • the working temperature is 120 ° C
  • the negative electrode is a solid metal aluminum sheet
  • the positive electrode is a composite anode material of graphite and titanium sulfide (1:1)
  • the conductive rod is a stainless steel rod
  • the separator is a GF/D glass fiber diaphragm.
  • the graph shows the charge-discharge specific capacity and coulombic efficiency of 1000 cycles at a current density of 2000 mAg -1 .
  • the electrolyte used in the figure is a supporting electrolyte of NaCl:AlCl 3 in a molar ratio of 1:1.5.
  • the working temperature is 120 ° C
  • the negative electrode is a solid metal aluminum sheet
  • the positive electrode is a composite anode material of graphite and titanium sulfide (1:1)
  • the conductive rod is a stainless steel rod
  • the separator is a GF/D glass fiber diaphragm.
  • the figure shows the charge-discharge specific capacity and coulombic efficiency of 1000 cycles at a current density of 2000 mAg -1 .
  • a block of graphite and titanium sulfide (mass ratio 1:1) composite material is processed into a square piece having a side length of 1000 mm and a thickness of 60 mm, and a thread having a depth of 100 mm and a diameter of 50 mm is machined on one side of the piece and passed through A 50 mm diameter stainless steel rod was threaded to serve as a conductive rod for the positive electrode composite. Then, a glass fiber separator was wrapped on the positive electrode composite material, and then a cubic electrolytic cell having a side length of 1200 mm and a depth of 1200 mm was used as a reaction vessel.
  • An aluminum ingot with a purity greater than 99% is selected and processed into a square piece having a side length of 1000 mm and a thickness of 50 mm, and a thread having a depth of 100 mm and a diameter of 30 mm is machined on one side of the sheet, and a stainless steel having a diameter of 30 mm is screwed.
  • the rod serves as a conductive rod for the negative aluminum sheet.
  • NaCl:AlCl 3 in a molar ratio of 1:1.5 was used as a supporting electrolyte. When the battery is assembled, a uniform electrolyte is added to the reaction vessel, and the thickness of the electrolyte is between 900 and 1000 mm.
  • the electrolytic cell was heated to a temperature of 120 °C.
  • the position of the positive electrode block to adjust the position of the positive electrode block, it is immersed in the electrolyte to a depth of 800 mm and soaked for a certain time, thereby completing the secondary aluminum ion molten salt battery of the present invention.
  • the blue triangle in the figure is the charging specific capacity
  • the red square is the discharge specific capacity
  • the black circle is the coulomb efficiency.
  • the charge and discharge specific capacity is about 60 mAhg -1 , and the battery capacity does not decrease with the increase of the number of cycles, and it is stable at 60 mAhg -1 , indicating that the aluminum ion secondary battery has good. Cyclic stability. And the Coulomb efficiency has been maintained above 90%, close to 100%. Explain that the battery has high power utilization.
  • a block of graphite and titanium sulfide (mass ratio 1:1) composite material is processed into a square piece having a side length of 1000 mm and a thickness of 60 mm, and a thread having a depth of 100 mm and a diameter of 50 mm is machined on one side of the piece and passed through A 50 mm diameter stainless steel rod was threaded to serve as a conductive rod for the positive electrode composite. Then, a glass fiber separator was wrapped on the positive electrode composite material, and then a cubic electrolytic cell having a side length of 1200 mm and a depth of 1200 mm was used as a reaction vessel.
  • An aluminum ingot with a purity greater than 99% is selected and processed into a square piece having a side length of 1000 mm and a thickness of 50 mm, and a thread having a depth of 100 mm and a diameter of 30 mm is machined on one side of the sheet, and a stainless steel having a diameter of 30 mm is screwed.
  • the rod serves as a conductive rod for the negative aluminum sheet.
  • LiCl:AlCl 3 in a molar ratio of 1:1.5 was used as a supporting electrolyte. When the battery is assembled, a uniform electrolyte is added to the reaction vessel, and the thickness of the electrolyte is between 900 and 1000 mm.
  • the electrolytic cell was heated to 150 ° C. Finally, by adjusting the position of the positive electrode block to adjust the position of the positive electrode block, it is immersed in the electrolyte to a depth of 800 mm and soaked for a certain time, thereby completing the secondary aluminum ion molten salt battery of the present invention.
  • the test results of the battery show that the battery has a high discharge specific capacity, about 70mAg -1 at a current density of 2000mAg -1 , and is still stable after 100 cycles, and the coulombic efficiency is greater than 95%, showing excellent cycle performance and Higher capacity
  • a block of graphite and titanium sulfide (mass ratio 1:1) composite material is processed into a square piece having a side length of 1000 mm and a thickness of 60 mm, and a thread having a depth of 100 mm and a diameter of 50 mm is machined on one side of the piece and passed through A 50 mm diameter stainless steel rod was threaded to serve as a conductive rod for the positive electrode composite. Then, a glass fiber separator was wrapped on the positive electrode composite material, and then a cubic electrolytic cell having a side length of 1200 mm and a depth of 1200 mm was used as a reaction vessel.
  • An aluminum ingot with a purity greater than 99% is selected and processed into a square piece having a side length of 1000 mm and a thickness of 50 mm, and a thread having a depth of 100 mm and a diameter of 30 mm is machined on one side of the sheet, and a stainless steel having a diameter of 30 mm is screwed.
  • the rod serves as a conductive rod for the negative aluminum sheet.
  • KCl:AlCl 3 with a molar ratio of 1:1.85 is a supporting electrolyte. When the battery is assembled, a uniform electrolyte is added to the reaction vessel, and the thickness of the electrolyte is between 900 and 1000 mm.
  • the electrolytic cell was heated to 170 ° C. Finally, by adjusting the position of the positive electrode block to adjust the position of the positive electrode block, it is immersed in the electrolyte to a depth of 800 mm and soaked for a certain time, thereby completing the secondary aluminum ion molten salt battery of the present invention.
  • the battery test results show that the battery has a high discharge specific capacity, about 65mAg -1 at a current density of 1500mAg -1 , and is still stable after 100 cycles, and the Coulomb efficiency is greater than 92%, showing excellent cycle performance and Higher capacity
  • a block of graphite and titanium sulfide (mass ratio 1:1) composite material is processed into a square piece having a side length of 1000 mm and a thickness of 60 mm, and a thread having a depth of 100 mm and a diameter of 50 mm is machined on one side of the piece and passed through A 50 mm diameter stainless steel rod was threaded to serve as a conductive rod for the positive electrode composite. Then, a glass fiber separator was wrapped on the positive electrode composite material, and then a cubic electrolytic cell having a side length of 1200 mm and a depth of 1200 mm was used as a reaction vessel.
  • An aluminum ingot with a purity greater than 99% is selected and processed into a square piece having a side length of 1000 mm and a thickness of 50 mm, and a thread having a depth of 100 mm and a diameter of 30 mm is machined on one side of the sheet, and a stainless steel having a diameter of 30 mm is screwed.
  • the rod serves as a conductive rod for the negative aluminum sheet.
  • CaCl 2 :AlCl 3 having a molar ratio of 1:4 was used as a supporting electrolyte. When the battery is assembled, a uniform electrolyte is added to the reaction vessel, and the thickness of the electrolyte is between 900 and 1000 mm.
  • the electrolytic cell was heated to 250 ° C. Finally, by adjusting the position of the positive electrode block to adjust the position of the positive electrode block, it is immersed in the electrolyte to a depth of 800 mm and soaked for a certain time, thereby completing the secondary aluminum ion molten salt battery of the present invention.
  • the test results of the battery show that the battery has a high discharge specific capacity, about 80mAg -1 at a current density of 1000mAg -1 , and is still stable after 100 cycles, and the coulombic efficiency is greater than 90%, showing excellent cycle performance and Higher capacity
  • the block of carbon nanotubes and titanium sulfide (mass ratio 1:1) composite material is processed into a square piece having a side length of 1000 mm and a thickness of 60 mm, and a thread having a depth of 100 mm and a diameter of 50 mm is machined on one side of the piece.
  • a 50 mm diameter stainless steel rod was threaded to serve as a conductive rod for the positive electrode composite.
  • a glass fiber separator was wrapped on the positive electrode composite material, and then a cubic electrolytic cell having a side length of 1200 mm and a depth of 1200 mm was used as a reaction vessel.
  • An aluminum ingot with a purity greater than 99% is selected and processed into a square piece having a side length of 1000 mm and a thickness of 50 mm, and a thread having a depth of 100 mm and a diameter of 30 mm is machined on one side of the sheet, and a stainless steel having a diameter of 30 mm is screwed.
  • the rod serves as a conductive rod for the negative aluminum sheet.
  • NaCl:AlCl 3 in a molar ratio of 1:1.5 was used as a supporting electrolyte. When the battery is assembled, a uniform electrolyte is added to the reaction vessel, and the thickness of the electrolyte is between 900 and 1000 mm.
  • the electrolytic cell was heated to a temperature of 120 °C.
  • the position of the positive electrode block to adjust the position of the positive electrode block, it is immersed in the electrolyte to a depth of 800 mm and soaked for a certain time, thereby completing the secondary aluminum ion molten salt battery of the present invention.
  • the test results of the battery show that the battery has a high discharge specific capacity, about 120mAg -1 at a current density of 500mAg -1 , and is still stable after 100 cycles, and the coulombic efficiency is more than 85%, showing excellent cycle performance and Higher capacity
  • the block of carbon nanotubes and molybdenum sulfide (mass ratio 1:1) composite material is processed into a square piece having a side length of 1000 mm and a thickness of 60 mm, and a thread having a depth of 100 mm and a diameter of 50 mm is machined on one side of the piece.
  • a 50 mm diameter stainless steel rod was threaded to serve as a conductive rod for the positive electrode composite.
  • a glass fiber separator was wrapped on the positive electrode composite material, and then a cubic electrolytic cell having a side length of 1200 mm and a depth of 1200 mm was used as a reaction vessel.
  • An aluminum ingot with a purity greater than 99% is selected and processed into a square piece having a side length of 1000 mm and a thickness of 50 mm, and a thread having a depth of 100 mm and a diameter of 30 mm is machined on one side of the sheet, and a stainless steel having a diameter of 30 mm is screwed.
  • the rod serves as a conductive rod for the negative aluminum sheet.
  • NaCl:AlCl 3 in a molar ratio of 1:1.5 was used as a supporting electrolyte. When the battery is assembled, a uniform electrolyte is added to the reaction vessel, and the thickness of the electrolyte is between 900 and 1000 mm.
  • the electrolytic cell was heated to a temperature of 120 °C.
  • the position of the positive electrode block to adjust the position of the positive electrode block, it is immersed in the electrolyte to a depth of 800 mm and soaked for a certain time, thereby completing the secondary aluminum ion molten salt battery of the present invention.
  • the test results of the battery show that the battery has a high discharge specific capacity, about 55mAg -1 at a current density of 2000mAg -1 , and is still stable after 100 cycles.
  • the Coulomb efficiency is greater than 98%, showing excellent cycle performance and Higher capacity
  • the block of carbon nanotubes and nickel sulfide (mass ratio 1:1) composite material is processed into a square piece having a side length of 1000 mm and a thickness of 60 mm, and a thread having a depth of 100 mm and a diameter of 50 mm is machined on one side of the piece.
  • a 50 mm diameter stainless steel rod was threaded to serve as a conductive rod for the positive electrode composite.
  • a glass fiber separator was wrapped on the positive electrode composite material, and then a cubic electrolytic cell having a side length of 1200 mm and a depth of 1200 mm was used as a reaction vessel.
  • An aluminum ingot with a purity greater than 99% is selected and processed into a square piece having a side length of 1000 mm and a thickness of 50 mm, and a thread having a depth of 100 mm and a diameter of 30 mm is machined on one side of the sheet, and a stainless steel having a diameter of 30 mm is screwed.
  • the rod serves as a conductive rod for the negative aluminum sheet.
  • NaCl:AlCl 3 in a molar ratio of 1:1.5 was used as a supporting electrolyte.
  • a uniform electrolyte is added to the reaction vessel, and the thickness of the electrolyte is between 2000 mm. After the assembly of the electrolysis device was completed, the electrolytic cell was heated to 170 ° C.
  • the positive electrode block by adjusting the position of the positive electrode block to adjust the position of the positive electrode block, it is immersed in the electrolyte to a depth of 800 mm and soaked for a certain time, thereby completing the secondary aluminum ion molten salt battery of the present invention.
  • the test results of the battery show that the battery has a high discharge specific capacity, about 50mAg -1 at a current density of 3000mAg -1 , and is still stable after 100 cycles, and the coulombic efficiency is greater than 98%, showing excellent cycle performance and Higher capacity
  • the block of carbon nanotubes and tungsten sulfide (mass ratio 1:1) composite material is processed into a square piece having a side length of 1000 mm and a thickness of 60 mm, and a thread having a depth of 100 mm and a diameter of 50 mm is machined on one side of the piece.
  • a 50 mm diameter stainless steel rod was threaded to serve as a conductive rod for the positive electrode composite.
  • a glass fiber separator was wrapped on the positive electrode composite material, and then a cubic electrolytic cell having a side length of 1200 mm and a depth of 1200 mm was used as a reaction vessel.
  • An aluminum ingot with a purity greater than 99% is selected and processed into a square piece having a side length of 1000 mm and a thickness of 50 mm, and a thread having a depth of 100 mm and a diameter of 30 mm is machined on one side of the sheet, and a stainless steel having a diameter of 30 mm is screwed.
  • the rod serves as a conductive rod for the negative aluminum sheet.
  • NaCl:AlCl 3 with a molar ratio of 1:1.5 was used as the supporting electrolyte, and 10% of LiAlBr 4 of the total mass of NaCl and AlCl 3 was further added.
  • the battery When the battery is assembled, a uniform electrolyte is added to the reaction vessel, and the thickness of the electrolyte is between 900 and 1000 mm. After the assembly of the electrolysis device was completed, the electrolytic cell was heated to 150 ° C. Finally, the positive electrode conductive rod was adjusted to adjust the position of the positive electrode block so as to be immersed in the electrolyte to a depth of 800 mm and soaked for a certain period of time, thereby completing the secondary aluminum ion molten salt battery of the present invention.
  • the test results of the battery show that the battery has a high discharge specific capacity, about 85mAg -1 at a current density of 1500mAg -1 , and is still stable after 100 cycles, with a Coulomb efficiency of more than 97%, showing excellent cycle performance and Higher capacity
  • a block of acetylene black and tungsten sulfide (mass ratio 4:6) composite material is processed into a square piece having a side length of 1000 mm and a thickness of 60 mm, and a thread having a depth of 100 mm and a diameter of 50 mm is machined on one side of the piece.
  • a 50 mm diameter stainless steel rod was threaded to serve as a conductive rod for the positive electrode composite.
  • a glass fiber separator was wrapped on the positive electrode composite material, and then a cubic electrolytic cell having a side length of 1200 mm and a depth of 1200 mm was used as a reaction vessel.
  • An aluminum ingot with a purity greater than 99% is selected and processed into a square piece having a side length of 1000 mm and a thickness of 50 mm, and a thread having a depth of 100 mm and a diameter of 30 mm is machined on one side of the sheet, and a stainless steel having a diameter of 30 mm is screwed.
  • the rod serves as a conductive rod for the negative aluminum sheet.
  • NaCl:AlCl 3 in a molar ratio of 1:1.5 was used as a supporting electrolyte, and 5% of NaAlCl 4 was added to the total mass of NaCl and AlCl 3 .
  • the battery When the battery is assembled, a uniform electrolyte is added to the reaction vessel, and the thickness of the electrolyte is between 900 and 1000 mm. After the assembly of the electrolysis device was completed, the electrolytic cell was heated to 160 ° C. Finally, by adjusting the position of the positive electrode block to adjust the position of the positive electrode block, it is immersed in the electrolyte to a depth of 800 mm and soaked for a certain time, thereby completing the secondary aluminum ion molten salt battery of the present invention.
  • the test results of the battery show that the battery has a high discharge specific capacity, about 95mAg -1 at a current density of 1000mAg -1 , and is still stable after 100 cycles, and the coulombic efficiency is greater than 96%, showing excellent cycle performance and Higher capacity
  • a block of acetylene black and titanium sulfide (mass ratio 2:8) composite material is processed into a square piece having a side length of 1000 mm and a thickness of 60 mm, and a thread having a depth of 100 mm and a diameter of 50 mm is machined on one side of the piece.
  • a 50 mm diameter stainless steel rod was threaded to serve as a conductive rod for the positive electrode composite.
  • a glass fiber separator was wrapped on the positive electrode composite material, and then a cubic electrolytic cell having a side length of 1200 mm and a depth of 1200 mm was used as a reaction vessel.
  • An aluminum ingot with a purity greater than 99% is selected and processed into a square piece having a side length of 1000 mm and a thickness of 50 mm, and a thread having a depth of 100 mm and a diameter of 30 mm is machined on one side of the sheet, and a stainless steel having a diameter of 30 mm is screwed.
  • the rod serves as a conductive rod for the negative aluminum sheet.
  • NaCl:AlCl 3 in a molar ratio of 1:1.5 was used as a supporting electrolyte.
  • a uniform electrolyte is added to the reaction vessel, and the thickness of the electrolyte is between 1000 mm. After the assembly of the electrolysis device was completed, the electrolytic cell was heated to 150 ° C.
  • the secondary aluminum conductive molten salt battery of the present invention is completed by adjusting the position of the positive electrode block to adjust the position of the positive electrode block to be immersed in the electrolyte to a depth of 800 mm and soaking for a certain period of time.
  • the test results of the battery show that the battery has a high discharge specific capacity, about 55mAg -1 at a current density of 2500mAg -1 , and is still stable after 100 cycles.
  • the Coulomb efficiency is greater than 96%, showing excellent cycle performance and Higher capacity.

Landscapes

  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

一种低温无机熔盐铝离子超级电容电池及其制备方法。所述铝离子超级电容电池包含正极、负极和电解质，其中正极活性物质为碳材料和过渡金属硫化物的复合物，负极为金属铝或其合金，电解质为氯化铝和碱金属或者碱土金属氯化物的混合熔盐体系，电解质还可以含有溴铝酸盐和氯铝酸盐添加剂。所述铝离子超级电容电池可快速充放电、容量高、效率高、循环稳定性好以及充放电特性优异，电极材料来源广泛、成本低、绿色环保。

Description

一种低温无机熔盐铝离子超级电容电池及其制备方法 技术领域
本发明属于新型绿色能源电池应用于电子产业、通信产业及电动车动力电池等领域，尤其涉及一种低温无机熔盐铝离子超级电容电池及其制备方法。
背景技术
近年来，环境污染和温室效应日益加剧，煤炭、石油和天然气等不可再生化石燃料日益枯竭，能源危机和环境保护成为世界面临的两大难题。因此，开发并利用清洁可再生能源成为了当前研究的热点，其中电能因其处于多种能源转换的核心阶段而成为了整个可再生能源开发和利用的关键。自日本SONY公司成功推出锂离子电池以来，锂离子电池便迅速在电子产品、动力能源、军事领域等多方面得到了广泛的应用，目前二次电池仍然以锂离子电池为主。但是由于锂资源的局限导致成本昂贵以及较大的安全隐患限制了锂离子电池的进一步发展。要将锂离子电池大规模应用于风能、太阳能以及潮汐能等绿色环保能源的能量转换与储存几乎是不可能完成的任务。另外，锂离子电池因负极枝状晶的生成所存在的安全隐患使得人们一直在寻求新的电池体系。近来，低温熔盐二次电池进入了人们的视线。相对于常温离子电池，低温熔融盐二次电池离子迁移率快，电极极化小、有利于能量的高效率储存与转换。本发明采用原料广泛且成本低廉的石墨以及过渡金属硫化物和金属铝作为电池正、负极，采用含铝离子的熔融卤化物为电解质，可有效并大规模应用于多种可再生清洁能源的储存于利用。
焦树强等在2013年采用过渡金属氧化物作为铝离子电池正极材料，这也是首次提出超价电池的概念。研究发现，尽管其电位平台较低，但起有较高的比容量和稳定的循环性能(Wang W,Jiang B,Xiong W,et al.A new cathode material for super-valent battery based on aluminium ion intercalation and deintercalation[J].Scientific reports,2013,3)。
焦树强等在2014年申请了中国发明专利No.CN201410419495.1报道了采用石墨类碳质材料作为铝离子电池的正极材料，高纯铝为负极材料的一种可充电铝离子二次电池，该团队对此类电池进行了一系列相关的研究工作，采用碳纸作为铝离子电池正极材料，循环100圈后，其剩余比容量高达66.92mAh g-1，而且 有较高的循环稳定性能(文献：Sun H,Wang W,Yu Z,et al.A new aluminium-ion battery with high voltage,high safety and low cost[J].Chemical Communications,2015,51(59):11892-11895)。最近，斯坦福大学的Dai等人发表在《Nature》杂志上的一篇名为“一种超快可充电铝离子电池”的文章再次引起了广泛的关注(文献：Lin M C,Gong M,Lu B,et al.An ultrafast rechargeable aluminium-ion battery[J].Nature,2015)，研究采用热解石墨和3维石墨泡沫作为铝离子电池正极材料，其比容量稳定在60mAh g-1以上。
焦树强团队近期申请的中国发明专利(No.CN201410592604.X和No.CN201510002870.7分别报道了采用层状结构的MoS2和WS2作为铝离子电池的正极材料，由于其特殊的S-M-S(M＝Mo、W)三层式层状结构，M-S原子间为共价键，层与层之间以弱的范德华力相连，这种材料，层内键作用强，而层间相对较弱，可以作为电化学嵌铝及其复杂离子电极材料。说明了金属硫化物作为铝离子电池正极材料的可行性。
发明内容
本发明提供一种可用于风能、太阳能、潮汐能等可再生清洁能源的能量储存与转换利用的熔盐电池，突出的充放电比容量，优异的循环性能、能量转换效率以及较好的安全性、清洁性使得其可大规模应用于多种绿色清洁能源的高效率储存与转换的低温无机熔盐铝离子超级电容电池及其制备方法。
为实现上述目的，本发明提供以下技术方案：一种低温无机熔盐铝离子超级电容电池，该电容电池包含正极、负极和电解质及电解池装置，其中，所述正极为碳材料和过渡金属硫化物的复合物，负极为固态金属铝或其固态合金，所述电解质为氯化铝和碱金属或者碱土金属氯化物的混合熔盐体系。
进一步，所述电解质的各组分的比例为：所述三氯化铝与碱金属氯化物或碱土金属氯化物的摩尔浓度比为：1～4:1；所述添加剂的加入量不超过三氯化铝与碱金属氯化物或碱土金属氯化物总质量的20％；所述碱金属包括LiCl、NaCl、KCl、RbCl或CsCl；所述碱土金属氯化物包括MgCl2、CaCl2或BaCl2；所述添加剂包括LiAlBr4、NaAlBr4、KAlBr4、LiAlCl4、NaAlCl4或KAlCl4:1。
进一步，所述正极的各组分的比例为：碳材料的质量百分比为10％～50％，过渡金属硫化物的质量百分比为50％～90％；所述碳材料包括：石墨、碳纸、碳 纤维纸、碳纳米管、石墨烯、膨胀石墨或炭黑；所述过渡金属硫化物包括：硫化镍，硫化钛，硫化铜，硫化铁，硫化铅，硫化锆，硫化钒，硫化铬，硫化钴或硫化钼。
进一步，所述正极或固态负极形状为片状、长方体状、立方体状，圆筒状块体或其它具有至少一个平面的不规则块体。
进一步，所述负极为固态金属铝或固态金属铝与金属镓、铜、铬、铁、镍、铅、铋、锡或银形成的二元或多元合金。
进一步，所述电容电池的工作温度为50-300℃。
本发明的另一目的是提供上述低温无机熔盐铝离子超级电容电池的制备方法，具体包括以下步骤：
步骤1.制备正极：将碳材料和过渡金属硫化物按照设计比例混合均匀用隔膜材料包裹后与正极耐高温导电杆采用螺纹、夹具、钩挂、镶嵌或耐高温金属丝捆绑的方式连接作为正极，备用；
步骤2.制备负极:将固态铝或铝合金采用螺纹、夹具、钩挂、镶嵌或耐高温金属丝捆绑的方式与负极导电杆连接作为负极；
步骤3.配制熔盐电解质体系：将三氯化铝与碱金属氯化物或碱土金属氯化物按照摩尔浓度比为：1～4:1分别称取，混合均匀，再加入一定量的添加剂，得到熔盐电解质体系，其中，添加剂的加入量不超过三氯化铝与碱金属氯化物或碱土金属氯化物总质量的20％；
步骤4.组装：将步骤3制备得到的熔盐电解质体系添加到反应容器中，铺设的厚度为100-5000mm，然后安装步骤1制备得到正极和步骤2制备得到负极，随后加热至50-300℃，最后，通过调节正极导电杆调剂正极块体位置，使其浸入电解质中浸泡一定时间，即得到无机熔盐铝离子二次超级电容电池。
进一步，所述负极耐高温导电杆为不锈钢、钼、钛、镍等包括但不仅限于它们的金属或合金制成。
进一步，所述三氯化铝、碱金属氯化物或碱土金属氯化物在无氧无水环境中磨成粒径为0.001-50mm颗粒。
进一步，所述熔盐电解质体系质的铺设厚度还可以为1000-2000mm。
本发明的有益效果是：由于采用上述技术方案，本发明使用碳材料和过渡金 属硫化物的复合物为正极，固态金属铝或合金作为负极，氯化铝和碱金属或者碱土金属氯化物的混合熔盐体系为电解质构成了一种熔盐铝离子二次超级电容电池。具有以下特点：以AlCl3作为电解质熔盐体系的组成部分，电解质熔盐体系中的铝离子的质量百分数为60％-78.2％。负极铝元素在地壳的储量丰富，价格便宜，大大降低了电池的制备成本；碳材料和过渡金属硫化物具备层状结构，利于铝元素的嵌入与脱出，同时具备优良的化学稳定性和热稳定性二次铝离子熔盐电池的循环稳定性、充放电比容量以及循环效率；熔融盐作为电解质，导电率高，热稳定性好，同时离子迁移率较高并具备较宽的电势窗口，可有效降低本发明二次铝离子熔盐电池内阻，从而提高能量转换效率。基于以上特点，本发明二次铝离子熔盐电池可安全可靠、清洁环保可大规模用于风能、太阳能、潮汐能等可再生清洁能源的能量储存与转换利用。
附图说明
图1为电解质是以摩尔比为1:1.5的NaCl：AlCl3为支持电解质。工作温度120℃，负极为固态金属铝片，正极为石墨和硫化钛(1：1)的复合阳极材料，导电杆为不锈钢杆，隔膜为GF/D玻璃纤维隔膜。图中为2000mAg-1的电流密度下，循环1000圈的充放电比容量和库伦效率的曲线示意图。
具体实施方式
下面结合附图和实施例对本发明进一步说明。
如图1所示，图中所用的电解质是以摩尔比为1:1.5的NaCl：AlCl3为支持电解质。工作温度120℃，负极为固态金属铝片，正极为石墨和硫化钛(1：1)的复合阳极材料，导电杆为不锈钢杆，隔膜为GF/D玻璃纤维隔膜。图中为2000mAg-1的电流密度下，循环1000圈的充放电比容量和库伦效率。
具体实施方式
本发明下面将通过具体实施例进行更详细的描述，但本发明的保护范围并不受限于这些实施例。
实施例1
将石墨和硫化钛(质量比1:1)复合材料的块体加工为边长1000mm，厚60mm的方片状块体，并在片体的一边加工出深100mm，直径50mm的螺纹，并通过 螺纹连接一根直径50mm的不锈钢棒作为正极复合材料的导电杆。然后在正极复合材料上包裹一层玻璃纤维隔膜，之后砌筑边长1200mm，深1200mm的立方体电解池作为反应容器。选取纯度大于99％的铝锭，将其加工为边长1000mm，厚50mm的方片状，并在片体的一边加工出深100mm，直径30mm的螺纹，并通过螺纹连接一根直径30mm的不锈钢棒作为负极铝片的导电杆。以摩尔比为1:1.5的NaCl：AlCl3为支持电解质。组装电池时，混合均匀的电解质添加反应容器中，电解质的厚度在900～1000mm之间。电解装置组装完成后，将电解池加热升温至120℃。最后，通过调节正极导电杆调剂正极块体位置，使其浸入电解质中800mm深并浸泡一定时间，至此完成本发明二次铝离子熔盐电池。如图1所示，图中蓝色三角为充电比容量，红色方框为放电比容量，黑色圈为库伦效率。从图中可以看出充、放电比容量大概在60mAhg-1左右，并且随着循环圈数的增加，电池的容量并没有降低，并且稳定在60mAhg-1，说明该铝离子二次电池有良好的循环稳定性。并且库伦效率一直都维持在90％以上，接近100％。说明该电池的电能利用率很高。
实施例2
将石墨和硫化钛(质量比1:1)复合材料的块体加工为边长1000mm，厚60mm的方片状块体，并在片体的一边加工出深100mm，直径50mm的螺纹，并通过螺纹连接一根直径50mm的不锈钢棒作为正极复合材料的导电杆。然后在正极复合材料上包裹一层玻璃纤维隔膜，之后砌筑边长1200mm，深1200mm的立方体电解池作为反应容器。选取纯度大于99％的铝锭，将其加工为边长1000mm，厚50mm的方片状，并在片体的一边加工出深100mm，直径30mm的螺纹，并通过螺纹连接一根直径30mm的不锈钢棒作为负极铝片的导电杆。以摩尔比为1:1.5的LiCl：AlCl3为支持电解质。组装电池时，混合均匀的电解质添加反应容器中，电解质的厚度在900～1000mm之间。电解装置组装完成后，将电解池加热升温至150℃。最后，通过调节正极导电杆调剂正极块体位置，使其浸入电解质中800mm深并浸泡一定时间，至此完成本发明二次铝离子熔盐电池。电池的测试结果显示该电池具有较高的放电比容量，在2000mAg-1的电流密度下约为70mAg-1，循环100圈之后仍然很稳定，库伦效率大于95％，表现出优异的循环性能和较高的容量
实施例3
将石墨和硫化钛(质量比1:1)复合材料的块体加工为边长1000mm，厚60mm的方片状块体，并在片体的一边加工出深100mm，直径50mm的螺纹，并通过螺纹连接一根直径50mm的不锈钢棒作为正极复合材料的导电杆。然后在正极复合材料上包裹一层玻璃纤维隔膜，之后砌筑边长1200mm，深1200mm的立方体电解池作为反应容器。选取纯度大于99％的铝锭，将其加工为边长1000mm，厚50mm的方片状，并在片体的一边加工出深100mm，直径30mm的螺纹，并通过螺纹连接一根直径30mm的不锈钢棒作为负极铝片的导电杆。以摩尔比为1:1.85的KCl：AlCl3为支持电解质。组装电池时，混合均匀的电解质添加反应容器中，电解质的厚度在900～1000mm之间。电解装置组装完成后，将电解池加热升温至170℃。最后，通过调节正极导电杆调剂正极块体位置，使其浸入电解质中800mm深并浸泡一定时间，至此完成本发明二次铝离子熔盐电池。电池的测试结果显示该电池具有较高的放电比容量，在1500mAg-1的电流密度下约为65mAg-1，循环100圈之后仍然很稳定，库伦效率大于92％，表现出优异的循环性能和较高的容量
实施例4
将石墨和硫化钛(质量比1:1)复合材料的块体加工为边长1000mm，厚60mm的方片状块体，并在片体的一边加工出深100mm，直径50mm的螺纹，并通过螺纹连接一根直径50mm的不锈钢棒作为正极复合材料的导电杆。然后在正极复合材料上包裹一层玻璃纤维隔膜，之后砌筑边长1200mm，深1200mm的立方体电解池作为反应容器。选取纯度大于99％的铝锭，将其加工为边长1000mm，厚50mm的方片状，并在片体的一边加工出深100mm，直径30mm的螺纹，并通过螺纹连接一根直径30mm的不锈钢棒作为负极铝片的导电杆。以摩尔比为1:4的CaCl2：AlCl3为支持电解质。组装电池时，混合均匀的电解质添加反应容器中，电解质的厚度在900～1000mm之间。电解装置组装完成后，将电解池加热升温至250℃。最后，通过调节正极导电杆调剂正极块体位置，使其浸入电解质中800mm深并浸泡一定时间，至此完成本发明二次铝离子熔盐电池。电池的测试结果显示该电池具有较高的放电比容量，在1000mAg-1的电流密度下约为80mAg-1，循环100圈之后仍然很稳定，库伦效率大于90％，表现出优异的循环性能和较高的容 量
实例5
将碳纳米管和硫化钛(质量比1:1)复合材料的块体加工为边长1000mm，厚60mm的方片状块体，并在片体的一边加工出深100mm，直径50mm的螺纹，并通过螺纹连接一根直径50mm的不锈钢棒作为正极复合材料的导电杆。然后在正极复合材料上包裹一层玻璃纤维隔膜，之后砌筑边长1200mm，深1200mm的立方体电解池作为反应容器。选取纯度大于99％的铝锭，将其加工为边长1000mm，厚50mm的方片状，并在片体的一边加工出深100mm，直径30mm的螺纹，并通过螺纹连接一根直径30mm的不锈钢棒作为负极铝片的导电杆。以摩尔比为1:1.5的NaCl：AlCl3为支持电解质。组装电池时，混合均匀的电解质添加反应容器中，电解质的厚度在900～1000mm之间。电解装置组装完成后，将电解池加热升温至120℃。最后，通过调节正极导电杆调剂正极块体位置，使其浸入电解质中800mm深并浸泡一定时间，至此完成本发明二次铝离子熔盐电池。电池的测试结果显示该电池具有较高的放电比容量，在500mAg-1的电流密度下约为120mAg-1，循环100圈之后仍然很稳定，库伦效率大于85％，表现出优异的循环性能和较高的容量
实例6
将碳纳米管和硫化钼(质量比1:1)复合材料的块体加工为边长1000mm，厚60mm的方片状块体，并在片体的一边加工出深100mm，直径50mm的螺纹，并通过螺纹连接一根直径50mm的不锈钢棒作为正极复合材料的导电杆。然后在正极复合材料上包裹一层玻璃纤维隔膜，之后砌筑边长1200mm，深1200mm的立方体电解池作为反应容器。选取纯度大于99％的铝锭，将其加工为边长1000mm，厚50mm的方片状，并在片体的一边加工出深100mm，直径30mm的螺纹，并通过螺纹连接一根直径30mm的不锈钢棒作为负极铝片的导电杆。以摩尔比为1:1.5的NaCl：AlCl3为支持电解质。组装电池时，混合均匀的电解质添加反应容器中，电解质的厚度在900～1000mm之间。电解装置组装完成后，将电解池加热升温至120℃。最后，通过调节正极导电杆调剂正极块体位置，使其浸入电解质中800mm深并浸泡一定时间，至此完成本发明二次铝离子熔盐电池。电池的测试结果显示该电池具有较高的放电比容量，在2000mAg-1的电流密度下 约为55mAg-1，循环100圈之后仍然很稳定，库伦效率大于98％，表现出优异的循环性能和较高的容量
实例7
将碳纳米管和硫化镍(质量比1:1)复合材料的块体加工为边长1000mm，厚60mm的方片状块体，并在片体的一边加工出深100mm，直径50mm的螺纹，并通过螺纹连接一根直径50mm的不锈钢棒作为正极复合材料的导电杆。然后在正极复合材料上包裹一层玻璃纤维隔膜，之后砌筑边长1200mm，深1200mm的立方体电解池作为反应容器。选取纯度大于99％的铝锭，将其加工为边长1000mm，厚50mm的方片状，并在片体的一边加工出深100mm，直径30mm的螺纹，并通过螺纹连接一根直径30mm的不锈钢棒作为负极铝片的导电杆。以摩尔比为1:1.5的NaCl：AlCl3为支持电解质。组装电池时，混合均匀的电解质添加反应容器中，电解质的厚度在2000mm之间。电解装置组装完成后，将电解池加热升温至170℃。最后，通过调节正极导电杆调剂正极块体位置，使其浸入电解质中800mm深并浸泡一定时间，至此完成本发明二次铝离子熔盐电池。电池的测试结果显示该电池具有较高的放电比容量，在3000mAg-1的电流密度下约为50mAg-1，循环100圈之后仍然很稳定，库伦效率大于98％，表现出优异的循环性能和较高的容量
实例8
将碳纳米管和硫化钨(质量比1:1)复合材料的块体加工为边长1000mm，厚60mm的方片状块体，并在片体的一边加工出深100mm，直径50mm的螺纹，并通过螺纹连接一根直径50mm的不锈钢棒作为正极复合材料的导电杆。然后在正极复合材料上包裹一层玻璃纤维隔膜，之后砌筑边长1200mm，深1200mm的立方体电解池作为反应容器。选取纯度大于99％的铝锭，将其加工为边长1000mm，厚50mm的方片状，并在片体的一边加工出深100mm，直径30mm的螺纹，并通过螺纹连接一根直径30mm的不锈钢棒作为负极铝片的导电杆。以摩尔比为1:1.5的NaCl：AlCl3为支持电解质，再添加NaCl和AlCl3总质量的10％的LiAlBr4。组装电池时，混合均匀的电解质添加反应容器中，电解质的厚度在900～1000mm之间。电解装置组装完成后，将电解池加热升温至150℃。最后，通过调节正极导电杆调剂正极块体位置，使其浸入电解质中800mm深并浸泡一 定时间，至此完成本发明二次铝离子熔盐电池。电池的测试结果显示该电池具有较高的放电比容量，在1500mAg-1的电流密度下约为85mAg-1，循环100圈之后仍然很稳定，库伦效率大于97％，表现出优异的循环性能和较高的容量
实例9
将乙炔碳黑和硫化钨(质量比4:6)复合材料的块体加工为边长1000mm，厚60mm的方片状块体，并在片体的一边加工出深100mm，直径50mm的螺纹，并通过螺纹连接一根直径50mm的不锈钢棒作为正极复合材料的导电杆。然后在正极复合材料上包裹一层玻璃纤维隔膜，之后砌筑边长1200mm，深1200mm的立方体电解池作为反应容器。选取纯度大于99％的铝锭，将其加工为边长1000mm，厚50mm的方片状，并在片体的一边加工出深100mm，直径30mm的螺纹，并通过螺纹连接一根直径30mm的不锈钢棒作为负极铝片的导电杆。以摩尔比为1:1.5的NaCl：AlCl3,为支持电解质，再添加NaCl和AlCl3总质量的5％的NaAlCl4。组装电池时，混合均匀的电解质添加反应容器中，电解质的厚度在900～1000mm之间。电解装置组装完成后，将电解池加热升温至160℃。最后，通过调节正极导电杆调剂正极块体位置，使其浸入电解质中800mm深并浸泡一定时间，至此完成本发明二次铝离子熔盐电池。电池的测试结果显示该电池具有较高的放电比容量，在1000mAg-1的电流密度下约为95mAg-1，循环100圈之后仍然很稳定，库伦效率大于96％，表现出优异的循环性能和较高的容量
实例10
将乙炔碳黑和硫化钛(质量比2:8)复合材料的块体加工为边长1000mm，厚60mm的方片状块体，并在片体的一边加工出深100mm，直径50mm的螺纹，并通过螺纹连接一根直径50mm的不锈钢棒作为正极复合材料的导电杆。然后在正极复合材料上包裹一层玻璃纤维隔膜，之后砌筑边长1200mm，深1200mm的立方体电解池作为反应容器。选取纯度大于99％的铝锭，将其加工为边长1000mm，厚50mm的方片状，并在片体的一边加工出深100mm，直径30mm的螺纹，并通过螺纹连接一根直径30mm的不锈钢棒作为负极铝片的导电杆。以摩尔比为1:1.5的NaCl：AlCl3为支持电解质。组装电池时，混合均匀的电解质添加反应容器中，电解质的厚度在1000mm之间。电解装置组装完成后，将电解池加热升温至150℃。最后，通过调节正极导电杆调剂正极块体位置，使其浸入电 解质中800mm深并浸泡一定时间，至此完成本发明二次铝离子熔盐电池。电池的测试结果显示该电池具有较高的放电比容量，在2500mAg-1的电流密度下约为55mAg-1，循环100圈之后仍然很稳定，库伦效率大于96％，表现出优异的循环性能和较高的容量。

Claims (10)

  1. 一种低温无机熔盐铝离子超级电容电池，该电容电池包含正极、负极和电解质及电解池装置，其特征在于，所述正极为碳材料和过渡金属硫化物的复合物，负极为固态金属铝或其固态合金，所述电解质为氯化铝和碱金属或者碱土金属氯化物的混合熔盐体系。
  2. 根据权利要求1所述的低温无机熔盐铝离子超级电容电池，其特征在于，所述电解质的各组分的比例为：所述三氯化铝与碱金属氯化物或碱土金属氯化物的摩尔浓度比为：1～4:1；所述添加剂的加入量不超过三氯化铝与碱金属氯化物或碱土金属氯化物总质量的20％；所述碱金属包括LiCl、NaCl、KCl、RbCl或CsCl；所述碱土金属氯化物包括MgCl2、CaCl2或BaCl2；所述添加剂包括LiAlBr4、NaAlBr4、KAlBr4、LiAlCl4、NaAlCl4或KAlCl4。
  3. 根据权利要求1所述的低温无机熔盐铝离子超级电容电池，其特征在于，所述正极的各组分的比例为：碳材料的质量百分比为10％～50％，过渡金属硫化物的质量百分比为50％～90％；所述碳材料包括：石墨、碳纸、碳纤维纸、碳纳米管、石墨烯、膨胀石墨或炭黑；所述过渡金属硫化物包括：硫化镍，硫化钛，硫化铜，硫化铁，硫化铅，硫化锆，硫化钒，硫化铬，硫化钴或硫化钼。
  4. 根据利要求1所述的低温无机熔盐铝离子超级电容电池，其特征在于，所述正极或固态负极形状为片状、长方体状、立方体状，圆筒状块体或其它具有至少一个平面的不规则块体。
  5. 根据利要求1所述的低温无机熔盐铝离子超级电容电池，其特征在于，所述负极为固态金属铝或固态金属铝与金属镓、铜、铬、铁、镍、铅、铋、锡或银形成的二元或多元合金。
  6. 根据利要求1所述的低温无机熔盐铝离子超级电容电池，其特征在于，所述电容电池的工作温度为50-300℃。
  7. 一种制备如权利要求1-6任一项权利要求所述的低温无机熔盐铝离子超级电容电池的方法，其特征在于，具体包括以下步骤：
    步骤1.制备正极：将碳材料和过渡金属硫化物按照设计比例混合均匀用隔膜材料包裹后与正极耐高温导电杆采用螺纹、夹具、钩挂、镶嵌或耐高温金属丝捆绑的方式连接作为正极，备用；
    步骤2.制备负极:将固态铝或铝合金采用螺纹、夹具、钩挂、镶嵌或耐高温 金属丝捆绑的方式与负极导电杆连接作为负极；
    步骤3.配制熔盐电解质体系：将三氯化铝与碱金属氯化物或碱土金属氯化物按照摩尔浓度比为：1～4:1分别称取，混合均匀，再加入一定量的添加剂，得到熔盐电解质体系，其中，添加剂的加入量不超过三氯化铝与碱金属氯化物或碱土金属氯化物总质量的20％；
    步骤4.组装：将步骤3制备得到的熔盐电解质体系添加到反应容器中，铺设的厚度为100-5000mm，然后安装步骤1制备得到正极和步骤2制备得到负极，随后加热至50-300℃，最后，通过调节正极导电杆调剂正极块体位置，使其浸入电解质中浸泡一定时间，即得到无机熔盐铝离子二次超级电容电池。
  8. 根据权利要求7所述的制备方法，其特征在于，所述负极耐高温导电杆为不锈钢、钼、钛、镍等包括但不仅限于它们的金属或合金制成。
  9. 根据权利要求7所述的制备方法，其特征在于，所述步骤3中，所述三氯化铝、碱金属氯化物或碱土金属氯化物在无氧无水环境中磨成粒径为0.001-50mm颗粒。
  10. 根据权利要求7所述的制备方法，其特征在于，所述熔盐电解质体系质的铺设厚度为1000-2000mm。
PCT/CN2016/072872 2016-01-05 2016-01-29 一种低温无机熔盐铝离子超级电容电池及其制备方法 WO2017117838A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201610007015.XA CN105632780A (zh) 2016-01-05 2016-01-05 一种低温无机熔盐铝离子超级电容电池及其制备方法
CN201610007015.X 2016-01-05

Publications (1)

Publication Number Publication Date
WO2017117838A1 true WO2017117838A1 (zh) 2017-07-13

Family

ID=56047594

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2016/072872 WO2017117838A1 (zh) 2016-01-05 2016-01-29 一种低温无机熔盐铝离子超级电容电池及其制备方法

Country Status (2)

Country Link
CN (1) CN105632780A (zh)
WO (1) WO2017117838A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114300767A (zh) * 2021-12-29 2022-04-08 华中科技大学 一种基于低温熔盐的碱金属固态电池界面改性方法与应用

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109244533B (zh) * 2017-12-13 2020-11-06 北京纳米能源与系统研究所 固态铝离子电池
CN108695551A (zh) * 2018-04-08 2018-10-23 湖北工业大学 一种熔盐法制备石榴石型固体电解质Li7La3Zr2O12块体的方法
CN108615933A (zh) * 2018-05-16 2018-10-02 东莞市振华新能源科技有限公司 一种基于新型正极材料的铝离子电池及其制备方法
CN109950640B (zh) * 2019-03-27 2021-07-13 西安交通大学 金属石墨中温储能电池及其制备方法
CN112072189B (zh) * 2019-06-11 2021-11-02 中国科学院物理研究所 LiFeCl4、NaFeCl4和KFeCl4中的一种或几种熔盐的应用以及熔盐电池
CN110890539B (zh) * 2019-11-18 2021-04-20 西安交通大学 一种软包金属石墨中温储能电池及其制备方法
CN114084906B (zh) * 2021-11-01 2024-04-26 西北工业大学 一种碱金属离子插层钒氧化物纳米带的快速制备方法及应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103579689A (zh) * 2012-08-09 2014-02-12 通用电气公司 电化学电池的制造方法
JP2014222609A (ja) * 2013-05-13 2014-11-27 学校法人 関西大学 アルミニウム二次電池
CN104701541A (zh) * 2015-01-06 2015-06-10 北京科技大学 一种ws2做正极的铝离子电池及其制备方法
CN104868179A (zh) * 2015-05-13 2015-08-26 北京科技大学 一种可充放电铝离子熔盐电池及其制备方法
CN104993130A (zh) * 2015-05-25 2015-10-21 石嘴山市天和创润新材料科技有限公司 一种非水溶液铝离子二次电池及其制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3650834A (en) * 1970-01-28 1972-03-21 Standard Oil Co Ohio Aluminum bromide fused salt battery
CN1197183C (zh) * 2000-03-01 2005-04-13 东芝株式会社 铝电池
US10128543B2 (en) * 2013-07-08 2018-11-13 Eos Energy Storage, Llc Molten metal rechargeable electrochemical cell
CN104393290B (zh) * 2014-10-29 2016-08-24 北京科技大学 一种采用MoS2为正极材料的铝离子电池及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103579689A (zh) * 2012-08-09 2014-02-12 通用电气公司 电化学电池的制造方法
JP2014222609A (ja) * 2013-05-13 2014-11-27 学校法人 関西大学 アルミニウム二次電池
CN104701541A (zh) * 2015-01-06 2015-06-10 北京科技大学 一种ws2做正极的铝离子电池及其制备方法
CN104868179A (zh) * 2015-05-13 2015-08-26 北京科技大学 一种可充放电铝离子熔盐电池及其制备方法
CN104993130A (zh) * 2015-05-25 2015-10-21 石嘴山市天和创润新材料科技有限公司 一种非水溶液铝离子二次电池及其制备方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114300767A (zh) * 2021-12-29 2022-04-08 华中科技大学 一种基于低温熔盐的碱金属固态电池界面改性方法与应用
CN114300767B (zh) * 2021-12-29 2023-08-25 华中科技大学 一种基于低温熔盐的碱金属固态电池界面改性方法与应用

Also Published As

Publication number Publication date
CN105632780A (zh) 2016-06-01

Similar Documents

Publication Publication Date Title
WO2017117838A1 (zh) 一种低温无机熔盐铝离子超级电容电池及其制备方法
CN101533900B (zh) 一种用于电化学可逆储锂的磷复合材料及其制备方法
CN101794907B (zh) 一种铝聚合物二次电池及其制备方法
CN109119603A (zh) 复合负极材料及其制备方法、锂离子二次电池负极极片和锂离子二次电池
CN109037626B (zh) 一种碱金属基负极及其制备方法和应用
CN107611411B (zh) 一种三维分级多孔氮掺杂碳包硅复合材料的制备方法及应用
WO2016180057A1 (zh) 一种可充放电铝离子熔盐电池及其制备方法
CN108899482B (zh) 铝离子电池及其正极材料
CN104795559A (zh) 一种高能量密度的锂离子动力电池
WO2018095202A1 (zh) 一种复合锂电池及其制备方法
CN104701541A (zh) 一种ws2做正极的铝离子电池及其制备方法
CN105633327B (zh) 一种TiS2为正极的铝离子二次电池及其制备工艺
CN111916721A (zh) 一种以镁锂合金为负极的镁硫二次电池
CN111082028A (zh) 一种容量高的负极材料、制备方法及锂离子电池
CN111320161A (zh) 一种沥青基碳纳米片的制备方法及其应用
CN108281620B (zh) 一种钠离子电池负极材料二氧化钛的制备方法
Lang et al. High‐performance porous lead/graphite composite electrode for bipolar lead‐acid batteries
CN109950640B (zh) 金属石墨中温储能电池及其制备方法
CN104176785A (zh) 一种Cu2+,Co2+,Ce4+,Ag+掺杂氟化铁复合正极材料及制备方法
CN104150542A (zh) 一种Cu2+,Co2+,Ag+掺杂氟化铁复合正极材料及制备方法
CN207504101U (zh) 一种石墨烯方形锂离子电池
CN205900715U (zh) 一种快充、快放、长寿锂离子动力电池
CN106410201B (zh) 一种铝离子电池负极材料及其制备方法和应用
CN102299375B (zh) 锂离子动力电池及锂离子动力电池的制备方法
CN104157836A (zh) 一种Cu2+,Co2+,Zr4+,Ag+掺杂氟化铁复合正极材料及制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16882983

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16882983

Country of ref document: EP

Kind code of ref document: A1