WO2011079482A1 - Batterie - Google Patents

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Publication number
WO2011079482A1
WO2011079482A1 PCT/CN2010/000177 CN2010000177W WO2011079482A1 WO 2011079482 A1 WO2011079482 A1 WO 2011079482A1 CN 2010000177 W CN2010000177 W CN 2010000177W WO 2011079482 A1 WO2011079482 A1 WO 2011079482A1
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Prior art keywords
battery
positive electrode
ion
negative electrode
electrolyte
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PCT/CN2010/000177
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English (en)
Chinese (zh)
Inventor
颜竞
刘昊
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万向电动汽车有限公司
万向集团公司
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Publication of WO2011079482A1 publication Critical patent/WO2011079482A1/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
    • 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
    • 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
    • H01M4/42—Alloys based on zinc
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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 invention belongs to the field of electrochemical energy storage, and particularly relates to a battery. Background technique
  • Rechargeable batteries that have been commercially used in history include lead-acid batteries, nickel-cadmium batteries, nickel-hydrogen batteries, lithium-ion batteries, etc., as well as nickel-zinc batteries, zinc-bromine batteries, etc., which are not fully mature.
  • lead-acid batteries and nickel-cadmium batteries are not accepted because of serious pollution and toxic.
  • Nickel-hydrogen batteries are still too expensive, and nickel resources are not rich, which limits their development.
  • Nickel-zinc batteries have been extensively studied in the 1960s and 1970s, but in alkaline environments, the dissolution of zinc anodes and the growth of dendrites are not effectively controlled, so it has been difficult to mature.
  • the problems encountered by zinc-bromine batteries are the diffusion of bromine, self-discharge and other factors.
  • batteries for electric vehicles are also fuel cells and metal air batteries.
  • fuel cells have powerful power and energy density close to that of internal combustion engine systems.
  • precious metal catalysts such as platinum.
  • its expensive price and scarcity of platinum resources made it destined to be unusable for a short time. It can be said that the fuel economy has stalled, leading to the collapse of the US hydrogen economy.
  • Other types of batteries, such as zinc-air batteries, are primary batteries that are difficult to use widely.
  • Lithium-ion batteries have been widely used since they were commercialized in the early 1990s.
  • the principle of such a battery is to obtain a potential difference by different deintercalation-insertion reaction potentials of lithium ions in the positive and negative active materials, and lithium ions flow between the positive and negative electrodes during charging and discharging, which is called a rocking chair battery.
  • the electrolyte can only use an organic solution which is stable over a wide voltage range as an electrolyte, and accordingly a suitable electrolyte is also very limited.
  • the improvement of rate discharge performance and the improvement of safety performance brought by new cathode materials lithium-ion batteries have gradually become more and more applicable in power tools, electric vehicles, and large-scale energy storage batteries.
  • lithium-ion batteries with lithium iron phosphate or lithium manganate are still not fully mature, mainly because they are expensive, and the control of moisture during the manufacturing process also leads to additional cost and instability of product consistency. These two factors have greatly hindered the large-scale application of lithium-ion batteries.
  • water-based lithium-ion batteries such as LiMn 2 O 4 as the positive electrode and vanadium oxide such as LiV 3 O 8 as the negative electrode.
  • the battery has high energy density (up to 60%-80% of lithium ion battery), high power density (expected to reach 200% of lithium ion battery, or even higher), easy to manufacture (no water is needed in the manufacturing process) Control), completely non-toxic, environmentally friendly, easy to recycle and low cost (the same capacity of the battery, is expected to reach 60% of lead-acid batteries, 20% of lithium-ion batteries, or even lower).
  • a battery comprising a positive electrode, a negative electrode and an electrolysis, wherein the active material of the positive electrode is one of a material capable of reversibly extracting-embeding ions or functional groups, and at least one of the metal elements is negatively used, and the electrolyte is capable of dissolving the electrolyte. At least one of a solvent which is ionized, wherein the electrolyte contains a metal ion of a positive electrode which can be eluted-embedded ions and a negative electrode active material.
  • the reversibility of the positive electrode is achieved by the extraction or embedding of the detachable-embedded ions on the positive active material
  • the reversibility of the negative electrode is achieved by electrochemical oxidation and reduction of the metal ion on the surface of the negative electrode.
  • the battery of the present invention includes a positive electrode, a negative electrode and an electrolyte in its core structure.
  • the active material of the positive electrode is a compound capable of eluting-intercalating lithium ions or sodium ions;
  • the negative electrode is a pure metal plate/foil, or a formed metal powder, and the metal is an active material of a negative electrode and can also serve as a negative electrode
  • the fluid is a solvent capable of dissolving the electrolyte and ionizing the electrolyte, such as water, an alcohol (such as methanol, ethanol), or the like, or another organic solvent capable of dissolving the electrolyte and ionizing the electrolyte, wherein the electrolyte A metal ion containing an ion-decomposing ion and a negative electrode active material which can be extracted in the positive electrode material.
  • the positive electrode active material of the battery of the present invention is a compound capable of eluting-embedding ions
  • the negative electrode active material is a metal having a different oxidation-reduction potential from the positive electrode active material deintercalation potential.
  • the positive electrode acquires electrons and intercalates ions; the negative active material metal loses electrons and dissolves in the electrolyte.
  • the electrolyte is a solution of multiple ions, Includes ions that can be deintercalated from the cathode material, to! a salt, a hydroxide, or other soluble corresponding metal compound of a metal contained in the negative electrode active material.
  • the charging and discharging working principle of the battery of the invention is as follows:
  • the positive electrode reaction is LiA a B e C — xe' - x
  • the negative electrode reaction is M x+ + xe' ⁇ M, LiAaB P C 3 ⁇ 4 - the general formula of the ion intercalating compound, and M is a kind of gold, which is an ion form of one or several metals.
  • Lithium ions or other detachable-embedded ions of the positive electrode are removed from the positive electrode active material, and the valence ions in the positive electrode active material are oxidized and lose electrons, and electrons pass from the positive electrode to the negative electrode via the external circuit.
  • a metal ion contained in the electrolyte obtains electrons on the surface of the negative electrode and is electrodeposited on the surface of the negative electrode in a metal form to achieve charging.
  • the discharge process is the opposite of the charging process.
  • LiMn 2 O 4 /Zn battery as an example (see Figures 2B-1 and 2B-2), the inventors further explain the working principle of the battery of the present invention: charging battery with LiMn 2 O 4 as positive electrode and zinc as negative electrode, charging When Li + ions in LiMn 2 O 4 are removed from the crystal lattice, one trivalent manganese loses an electron to be oxidized, LiMn 2 O 4 becomes a form of Li ⁇ Mi ⁇ O, and at the same time, zinc ions in the electrolyte get electrons. It is reduced and deposited on the surface of the metal zinc.
  • the positive reaction is
  • the negative electrode reaction is Zn 2+ + xe' ⁇ (x/2) Zn.
  • the discharge process is the reverse process of the charging process, that is, the zero-valent zinc of the negative electrode is oxidized and dissolved, and the positive electrode obtains electrons and is inserted into the lithium-ion ICP, and when discharged (as shown in FIG. 2B-2), the positive electrode reaction is
  • the reversible de-intercalation-intercalating material comprises a compound capable of deintercalating-embedded lithium, sodium plasma.
  • the positive electrode active material of the present invention is a compound capable of eluting-intercalating lithium ions, such as LiMn 2 O 4 , LiFePO 4 , LiCoO 2 Li xPO 4 , LiM x SiO y (wherein M is a variable metal) ) Binary materials or ternary material compounds.
  • lithium ions can be extracted-incorporated into compounds such as LiV 3 0 8 , etc., sodium ion-extractable-embedded compounds such as NaVPO 4 F, and the like, and can be ejected-embedded.
  • the ionic, functional group compounds all have similar functions and are also suitable for the positive electrode structure of the battery of the present invention.
  • the battery according to the present invention wherein the extractable-intercalating lithium ion-containing compound is selected from the group consisting of a layered structural compound, a spinel structure compound or an olivine structure compound, and other lithium and sodium ions are detachable. At least one of the embedded compounds.
  • a battery according to the present invention wherein the layered structural compound has a general formula of Wherein, 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 0.5, M is at least one selected from the group consisting of Co, Ni, and Mn, and M' is at least one selected from the group consisting of Mg, Ti, Cr, V, Zn, Zr, Si, or Ai.
  • M is at least one selected from the group consisting of Co, Ni, and Mn
  • M' is at least one selected from the group consisting of Mg, Ti, Cr, V, Zn, Zr, Si, or Ai.
  • LiFeSiO 4 or the like LiFeSiO 4 or the like.
  • the battery according to the present invention wherein the spinel structure compound has a general formula of Li x Mn y M z O k , wherein 0.5 ⁇ x ⁇ 3, 0 ⁇ y ⁇ 3 0 ⁇ z ⁇ 3, 0 ⁇ k ⁇ 8, M is at least one selected from the group consisting of Mg, Ti, Cr, V, Zn, Zr, Si or Al.
  • M is at least one selected from the group consisting of Mg, Ti, Cr, V, Zn, Zr, Si or Al.
  • LiV 3 O 8 LiMnSiO 4 and the like.
  • the battery of the olivine structure has a general formula of Li x M 2 _ y M' y (XO 4 ) n .
  • M is a transition metal element
  • M' is at least one selected from the group consisting of Mg, Ti, Cr, V or A1
  • X is selected from S, P or Si.
  • Li 3 V 2 (PO 4 ) 3 Li 3 V 2 (PO 4 ) 3 .
  • the battery according to the present invention wherein the negative electrode is made of a metal element selected from the group consisting of
  • Cu, Ag, Fe, Zn, Sn, Al or Ni may be specifically used as a negative electrode of a metal elementary plate, a foamed metal, or a shaped metal powder.
  • the battery according to the present invention wherein the positive electrode of the battery comprises a current collector, which uses at least one of stainless steel, carbon fiber, graphite and other electrochemically stable electron good conductors.
  • a current collector which uses at least one of stainless steel, carbon fiber, graphite and other electrochemically stable electron good conductors.
  • the inventors have also found that with a completely chemically inert carbon-based material as the positive current collector, the cycle performance of the battery is much better than that of stainless steel as the positive current collector.
  • the electrolyte is a chloride of lithium and a chloride of an anode active material.
  • the electrolyte is a sulfate of lithium and a sulfate of a negative electrode active material.
  • the electrolyte is water, and 1 M lithium ion and 5 M negative electrode active material ions are dissolved.
  • the electrolytic solution is methanol, and 1 M lithium ion and 5 M negative electrode active material ion are dissolved.
  • the electrolytic solution is ethanol, and 1 M lithium ion and 5 M negative electrode active material ion are dissolved.
  • the battery of the present invention is made of inexpensive LiMn 2 O 4 , a conductive agent, and a binder, and is bonded to a graphite current collector, conductive carbon paper, or the like as a positive electrode; and the metal zinc or zinc powder is a negative electrode.
  • the electrolyte includes lM Li + ions and 5M Zn 2+ ions.
  • the conductive agent is graphite and the binder is a PTFE emulsion.
  • the separator may not be used.
  • the separator is an organic or inorganic porous material, and the separator has a pore diameter of 0.001-1 ⁇ m.
  • the present invention has the following advantages:
  • Cycle life unit energy energy density resource rich environment friendly (time) cost* * :* sex as a power battery lead-acid battery 300 30% 30% rich, lead toxic for the previous generation mass production battery
  • NiMH battery 1000 80% 60% Nickel resources are not nickel for toxic and bare nickel-cadmium batteries 1000 50% 40% Nickel resources are not impossible Nickel-zinc battery 300 30% 50% Nickel resources are not temporarily unavailable Zinc-bromine battery 2000 30% 40% Rich, bromine corrosive can not be mass produced temporarily
  • Lithium-ion battery 2000 100% 100% rich, relatively friendly
  • the battery of the invention 1000 or more 20% 60%-70% rich, can be very friendly
  • the unit energy cost is calculated based on the current lithium battery.
  • the battery of the present invention is easy to manufacture, requires no moisture control during the manufacturing process, is easy to recycle, and is inexpensive.
  • FIG. 1 is a schematic view showing the structure of a battery of the present invention, wherein 1 is a positive electrode current collector, 2 is a positive electrode active material, 3 is a negative electrode active material as a current collector, and 4 is an electrolyte solution.
  • FIG. 2A is a schematic view showing the charging operation principle of the battery of the present invention in which the positive electrode material is LiA a B e C A .
  • FIG. 2B-1 and 2B-2 are schematic diagrams showing the working principle of the LiMn 2 O 4 /Zn battery of the present invention, wherein FIG. 2B-1 is a schematic diagram of a battery charging process; and FIG. 2B-2 is a schematic diagram of a battery discharging process.
  • FIG. 3 is a graph showing the first charge and discharge of a LiMn 2 O 4 /Zn battery according to Embodiment 1 of the present invention, wherein 1 is a charge profile and 2 is a discharge curve.
  • Figure 4 is a graph showing the cycle performance of a LiMn 2 04/i3 ⁇ 4 battery of Example 1 of the present invention.
  • Figure 5 is a graph showing the cycle performance of a LiFePO 4 /Zn battery according to Example 3 of the present invention.
  • Fig. 6 is a graph showing the cycle performance of a NaVPO ⁇ /Zn battery of Example 4 of the present invention.
  • Figure 7 is a graph showing the cycle performance of a LiMn 2 O 4 /foam nickel battery of Example 7 of the present invention.
  • Figure 8 is a graph showing the cycle performance of a LiMn 2 O 4 /Zn battery according to Example 14 of the present invention.
  • Figure 9 is a graph showing the relationship between charge and discharge efficiency and charge current multiplication of LiMn 2 O 4 /Zn battery in Example 20 of the present invention.
  • LiMn 2 0 4 is used as the positive electrode active material, and is uniformly mixed according to the positive electrode active material 88 wt%: conductive carbon black 8 wt%: adhesive PTFE (polytetrafluoroethylene) 4 wt%, and cut into a diameter of 12 mm and a thickness of 0.1-0.2 mm. The wafer is pressed onto a graphite current collector to form a positive electrode.
  • the negative electrode active material was metal zinc having a width of 15 mm and a thickness of 1 mm, and also served as a current collector.
  • the positive and negative electrodes are separated by 5 mm and have no diaphragm.
  • the electrolytic solution was a mixed aqueous solution of lithium chloride and zinc chloride containing 1 mol/L of lithium ion and 5 mol/L of zinc ion.
  • the cycle test was carried out under a voltage range of U-2.05 V and a charge-discharge current of 0.5 C.
  • Figure 1 shows the basic structure of a battery.
  • the first charge and discharge curve is shown in Figure 3, and the battery cycle performance is shown in Figure 4. It can be seen that the charge and discharge curve of the battery is very similar to that of the lithium ion battery of the organic electrolyte system, except that the platform is lower. From the perspective of the test battery, the cycle performance is also excellent.
  • a battery was fabricated in the same manner as in Example 1, except that LiCoO 2 was used as the positive electrode active material, and the cycle operating voltage ranged from 1.3-1.95 V.
  • the battery cycle performance test results are shown in Table 1.
  • a battery was fabricated in the same manner as in Example 1, except that LiFePO 4 was used as the positive electrode active material, and the cycle operating voltage ranged from 0.8 to 1.6 V.
  • the battery cycle performance test results are shown in Table 1 and Figure 5.
  • a battery was fabricated in the same manner as in Example 1, except that NaVPO 4 F was used as a positive electrode active material, and the cycle operating voltage ranged from 1.3 to 2.0 V.
  • the battery cycle performance test results are shown in Table 1 and Figure 6.
  • a battery was fabricated in the same manner as in Example 1, except that LiMn 2 0 4 and LiCo0 2 were mixed at a mass ratio of 1:1 as a positive electrode active material, and the cycle operating voltage ranged from 1.3 to 2.05 V.
  • the test results of charge and discharge and battery cycle performance are shown in Table 1. Capacity retention test
  • the batteries of the above Examples 1-5 were subjected to a cyclic charge discharge operation to detect the battery capacity retention rate after 30 cycles. First, the battery is charged at a fixed current of 0.5 C rate until the voltage reaches the upper limit, and then the battery is discharged at a fixed current of 0.5 C rate until the voltage reaches the lower limit. So repeating this week.
  • Table 1 below shows the battery performance exhibited by several different positive electrode materials and metallic zinc as counter electrodes.
  • LiMn 2 O 4 is used as the positive electrode active material, and the first charge and discharge curve of the metal zinc as the counter electrode is shown in FIG. 3 , and the cycle performance of the battery is shown in FIG. 4 .
  • Table 1 it can be seen that for the more mature cathode materials (LiMn 2 0 4 , LiCo0 2 and LiMn 2 0 4 /LiCo0 2 ), the electrochemical performance is better than that of other materials (LiFeP0 4 , NaVP0 4 ). F) It is much better.
  • LiMn 2 0 4 is used as the positive electrode active material, and is uniformly mixed according to the positive electrode active material 88 wt %: conductive carbon black 8 wt %: adhesive PTFE 4 wt%, and cut into discs having a diameter of 12 mm and a thickness of 0.1-0.2 mm, and pressed at On the graphite current collector, the positive electrode is formed;
  • the negative electrode active material is a manganese-coated zinc plate having a width of 15 mm and a thickness of 0.5-lmm (wherein the reduction property of zinc is not as strong as that of manganese, and does not participate in the reaction during charge and discharge, but acts as a current collector).
  • the positive and negative electrodes are separated by 5 mm and have no diaphragm.
  • the electrolytic solution was a mixed aqueous solution of lithium chloride and manganese chloride containing 1 md/L of lithium ion and 5 mol/L of manganese ion.
  • the cycle test was performed with a voltage range of 1.3-2.2 V and a charge-discharge current of 0.5 C.
  • a battery was fabricated in the same manner as in Example 6, except that instead of a manganese-coated zinc plate as a negative electrode, a nickel chloride containing 5 mol/L of nickel ions was replaced by nickel chloride containing 5 mol/L of nickel ions.
  • the aqueous solution was used as an electrolyte for a cycle test between a voltage range of 0.8-L5V and a charge-discharge current of 0.5C.
  • the results of the battery cycle performance test are shown in Table 2 and Figure 7.
  • a battery was fabricated in the same manner as in Example 6, except that an iron sheet was used instead of the manganese-coated zinc plate as the negative electrode, and accordingly, an aqueous solution of manganese chloride containing 5 mol of L manganese ions was replaced by ferric chloride containing 5 mol of iron ions.
  • the liquid is subjected to a cycle test in a voltage range of 1.3 to 2.0 V and a charge and discharge current of 0.5 C.
  • a battery was fabricated in the same manner as in Example 6, except that a cadmium sheet was used instead of the manganese-coated zinc sheet as a negative electrode, and a calcium chloride solution containing 5 mol/L of manganese ions was replaced by cadmium chloride containing 5 mol/L of cadmium ions.
  • a cycle test was performed with a voltage range of 1.3 to 2.0 V and a charge and discharge current of 0.5 C.
  • a battery was fabricated in the same manner as in Example 6, except that the pressed zinc powder was used instead of the manganese-coated zinc sheet as the negative electrode, and the test method was the same as in Example 2.
  • a battery was fabricated in the same manner as in Example 6, except that zinc oxide was used instead of the manganese-coated zinc sheet as the negative electrode, and the test method was the same as in Example 2.
  • the batteries in the above Examples 1 and 6-11 were subjected to a cyclic charge discharge operation to detect the capacity retention rate after 30 cycles. First, the battery is charged at a fixed current of 0.5 C rate until the voltage reaches the upper limit, and then the battery is discharged at a fixed current of 0.5 C rate until the voltage reaches the lower limit. So repeating this week.
  • Table 2 below shows the battery performance exhibited by the negative electrodes of several different metals and LiMn 2 O 4 as the positive electrode active material counter electrode.
  • a battery was fabricated in the same manner as in Example 1, except that an aqueous solution of lithium acetate containing 1 mol of lithium ion and zinc acetate containing 3 mol/L of zinc ion was used as an electrolytic solution, and the cycle operating voltage range was 1.3-2.05V.
  • a battery was fabricated in the same manner as in Example 1, except that lithium acetate containing 1 mol/L of lithium ion and methanol solution of zinc acetate containing 3 mol/L of zinc ion were used as the electrolyte, and the cycle operating voltage range was 1.3-2.05V. .
  • Example 14 A battery was fabricated in the same manner as in Example 1, except that lithium acetate containing 1 mol/L of lithium ion and ethanol solution of zinc acetate containing 3 mol/L of zinc ion were used as a solution, and the cycle operating voltage range was 1.3-2.05. V.
  • the battery cycle performance test results are shown in Table 3 and Figure 8. ;
  • a battery was fabricated in the same manner as in Example 1, except that an aqueous solution of lithium sulfate containing 1 mol/L of lithium ion and zinc sulfate containing 5 mol/L of zinc ion was used as an electrolytic solution, and the cycle operating voltage range was 1.3-2.05V.
  • a battery was fabricated in the same manner as in Example 1, except that a 316L type stainless steel having a thickness of 1 mm was used instead of the graphite sheet as a positive electrode active material current collector.
  • a battery was fabricated in the same manner as in Example 1, except that a 304 type stainless steel having a thickness of 1 mm was used instead of the graphite sheet as a positive electrode active material current collector. '
  • a battery was fabricated in the same manner as in Example 1, except that a carbon fiber cloth (thickness of about 0.1 mm) was used instead of the graphite sheet as a positive electrode active material current collector.
  • the inventors have also examined the electrical properties of a variety of other lithium ion-embedded compounds and metals as counter electrodes. Although the cycle performance of these combinations is quite different, they all form batteries and the charge and discharge mechanisms are basically the same, which are in accordance with the principle of charge and discharge of the battery of the present invention.
  • Table 5 shows the discharge open circuit voltages of the batteries composed of various electrode compositions.
  • Table 5 shows the open circuit voltage of the battery with different positive and negative poles
  • the positive and negative electrodes listed in Table 5 are only a small portion of the positive and negative electrodes that may be used in the battery of the present invention. Since there are many possible forms of such batteries in accordance with the principles of the present invention, particularly positive electrode materials, it may include sodium ion intercalation compounds which are not yet matured, as well as certain functional group deintercalation compounds and the like.
  • the battery may be accompanied by a series of side reactions such as decomposition of water, etc., while charging the battery.
  • a battery was fabricated in the same manner as in Example 1 to operate the battery at different charge and discharge current rates to obtain different charge and discharge current efficiencies. As a result, as shown in Fig. 9, a charge and discharge efficiency of 91% or more can be obtained at a suitable charge rate.

Abstract

L'invention se rapporte au domaine du stockage électrochimique d'énergie, et concerne une batterie. Ladite batterie comprend une électrode positive, une électrode négative et un électrolyte. Le matériau actif de l'électrode positive consiste en un type de matériau capable d'intercalage et de désintercalage réversibles. L'électrode négative se compose de métal. L'électrolyte consiste en une solution comprenant un ion capable d'intercalage et de désintercalage dans l'électrode positive, et un ion du métal de l'électrode négative. La réversibilité de l'électrode positive de la batterie dépend de l'intercalage ou du désintercalage de l'ion dans le matériau actif positif. La réversibilité de l'électrode négative dépend de l'électro-déposition et de la dissolution de l'ion métallique dans la surface de l'électrode négative. La batterie de la présente invention est moins nocive pour l'environnement que les batteries plomb-acide. Cette batterie est moins chère et possède une densité d'énergie plus élevée que les batteries utilisant du nickel pour l'électrode positive. Cette batterie ne présente pas les problèmes de déchargement automatique que l'on trouve dans les cellules zinc-bromure, et est moins onéreuse qu'une batterie Li-ion. Cette batterie est facile à fabriquer et à entretenir, et on peut s'attendre à ce qu'elle remplace les batteries plomb-acide dans peu de temps et qu'elle soit utilisée dans les véhicules électriques et les projets de stockage d'énergie à grande échelle.
PCT/CN2010/000177 2009-12-29 2010-02-08 Batterie WO2011079482A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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US9680154B2 (en) 2011-06-03 2017-06-13 Positec Power Tools (Suzhou) Co., Ltd. Battery

Families Citing this family (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN110752343B (zh) * 2019-10-22 2022-09-20 华南理工大学 一种镍离子电池正极及制备方法、镍离子电池与组装方法
CN111916720B (zh) * 2020-07-30 2021-06-29 山东大学 水系可充锌离子电池合金型负极材料及其制备方法与应用
CN114864950A (zh) * 2022-05-24 2022-08-05 山东合泰新能源有限公司 一种电极集流体及其制备方法和锌镍电池

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1097526A (zh) * 1993-07-10 1995-01-18 北京大学 二次锂离子水溶液电池
CN1674347A (zh) * 2005-04-21 2005-09-28 复旦大学 混合型水系锂离子电池
CN101154745A (zh) * 2007-09-20 2008-04-02 复旦大学 一种水系可充锂或钠离子电池
CN101262056A (zh) * 2007-03-08 2008-09-10 复旦大学 一种水溶液可充锂离子电池

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101087018A (zh) * 2007-06-28 2007-12-12 复旦大学 一种水溶液可充钠离子电池

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1097526A (zh) * 1993-07-10 1995-01-18 北京大学 二次锂离子水溶液电池
CN1674347A (zh) * 2005-04-21 2005-09-28 复旦大学 混合型水系锂离子电池
CN101262056A (zh) * 2007-03-08 2008-09-10 复旦大学 一种水溶液可充锂离子电池
CN101154745A (zh) * 2007-09-20 2008-04-02 复旦大学 一种水系可充锂或钠离子电池

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
XIA Y. Y. ET AL.: "Research progress of aqueous electrolyte Li-ion battery", CHINESE JOURNAL OF POWER SOURCES, vol. 32, no. 7, July 2008 (2008-07-01), pages 431 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9680154B2 (en) 2011-06-03 2017-06-13 Positec Power Tools (Suzhou) Co., Ltd. Battery
US10727491B2 (en) 2011-06-03 2020-07-28 Positec Power Tools (Suzhou) Co. Ltd. Battery
CN104347894A (zh) * 2013-08-02 2015-02-11 中国人民解放军63971部队 一种沉积型水系锂离子电池

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