WO2018170928A1 - 一种二次电池负极及其制备方法和二次电池 - Google Patents

一种二次电池负极及其制备方法和二次电池 Download PDF

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WO2018170928A1
WO2018170928A1 PCT/CN2017/078206 CN2017078206W WO2018170928A1 WO 2018170928 A1 WO2018170928 A1 WO 2018170928A1 CN 2017078206 W CN2017078206 W CN 2017078206W WO 2018170928 A1 WO2018170928 A1 WO 2018170928A1
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phosphate
negative electrode
metal
metal foil
secondary battery
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PCT/CN2017/078206
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English (en)
French (fr)
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唐永炳
谢呈德
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深圳中科瑞能实业有限公司
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Priority to PCT/CN2017/078206 priority Critical patent/WO2018170928A1/zh
Priority to US16/495,065 priority patent/US11189835B2/en
Publication of WO2018170928A1 publication Critical patent/WO2018170928A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H01M4/662—Alloys
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/049—Manufacturing of an active layer by chemical means
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H01M2300/0042—Four or more solvents
    • 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 secondary batteries, and in particular to a secondary battery negative electrode, a method for preparing the same, and a secondary battery.
  • the research team used aluminum foil as the negative electrode for the new high-efficiency battery.
  • This new high-efficiency battery system battery has higher specific energy density and lower cost. Therefore, this new high-efficiency battery has great application prospects.
  • the research team fully recognized the problems in using aluminum foil as the negative electrode tab, and proposed to process the aluminum foil into a carbon-coated porous aluminum foil to solve the problem of volume expansion and electrolyte compatibility of the aluminum foil.
  • the results of their research show that the solution they provide can effectively solve the problem of aluminum foil as a negative electrode.
  • the carbon material is coated on the surface of the aluminum foil, the compatibility between the negative electrode and the electrolytic solution is improved, but there is also a problem that the electrolytic solution is easily decomposed to form a solid electrolyte membrane to consume the electrolytic solution. Moreover, the carbon coating method has the problems of complicated processing technology and high processing cost.
  • the present invention proposes to improve the charge and discharge efficiency, cycle performance, and safety performance of a battery by providing a dense metal phosphate film on the surface of the metal foil.
  • a first aspect of the present invention provides a secondary battery negative electrode comprising a metal foil and a dense metal phosphate film disposed on a surface of the metal foil, the metal foil simultaneously serving as a negative electrode current collector and a negative electrode active material, the metal foil
  • the material includes any one of aluminum, copper, iron, tin, zinc, nickel, manganese, lead, antimony, cadmium and antimony, or an alloy containing at least one of the above metal elements;
  • the material of the metal phosphate film comprises phosphoric acid One or more of aluminum, copper phosphate, iron phosphate, tin phosphate, zinc phosphate, nickel phosphate, manganese phosphate, lead phosphate, strontium phosphate, cadmium phosphate, and strontium phosphate.
  • the metal source in the metal phosphate film is the same as the metal element in the metal foil.
  • the surface layer of the metal foil has a three-dimensional porous structure, and the porous pore size is from 10 nm to 20 ⁇ m.
  • the surface layer has a thickness of 1 nm to 10 ⁇ m, and a thickness ratio of the surface layer to the metal foil is 1:10-10000.
  • the metal phosphate film has a thickness of 1 nm to 3 ⁇ m, and a ratio of the thickness of the metal phosphate film to the thickness of the metal foil is 1:30 to 10,000.
  • the surface of the metal foil in the negative electrode of the secondary battery is provided with a metal oxide film in which metal ions such as lithium ions can migrate.
  • the metal phosphate membrane functions like a solid electrolyte membrane; improves the compatibility of the anode and the electrolyte, reduces the decomposition of the electrolyte, and improves the charge and discharge efficiency, battery cycle performance, high and low temperature performance, and safety performance of the battery.
  • a second aspect of the present invention provides a method for preparing a secondary battery negative electrode, comprising:
  • the secondary battery negative electrode includes a metal foil and a dense metal phosphate film disposed on the surface of the metal foil, the metal foil simultaneously serving as a negative electrode current collector and a negative electrode active material, and the material of the metal foil includes aluminum, copper, Any one of iron, tin, zinc, nickel, manganese, lead, antimony, cadmium and antimony, or an alloy containing at least one of the above metal elements; the material of the metal phosphate film comprises aluminum phosphate, copper phosphate, phosphoric acid One or more of iron, tin phosphate, zinc phosphate, nickel phosphate, manganese phosphate, lead phosphate, strontium phosphate, cadmium phosphate, and strontium phosphate.
  • the chemical reaction between the metal foil raw material and the phosphate-containing solution comprises:
  • the metal foil raw material is immersed in the phosphate-containing solution, and immersed at a temperature of 0 ° C - 80 ° C for 1 minute - 600 minutes; after the immersion is finished, washed with water and dried to obtain a secondary battery negative electrode.
  • the phosphate-containing solution comprises at least one of a phosphoric acid solution, a dihydrogen phosphate solution, a monohydrogen phosphate solution, a pyrophosphoric acid solution, a pyrophosphate solution, a metaphosphoric acid solution, and a metaphosphate solution;
  • the mass fraction of the solute in the phosphate-containing solution is 5%-85%.
  • the drying operation comprises: drying at 40 ° C - 120 ° C for 30 minutes - 600 minutes.
  • the preparation method provided by the second aspect of the invention is simple and easy to operate, has low cost, can be industrially produced, and is easy to produce a secondary battery negative electrode with high product consistency, uniform structure and stable performance.
  • a third aspect of the invention provides a secondary battery comprising a positive electrode, an electrolytic solution, a separator, and the negative electrode according to the above first aspect of the invention.
  • the electrolyte comprises an electrolyte and a solvent, the electrolyte comprising one or more of a lithium salt, a sodium salt, a potassium salt, a magnesium salt and a calcium salt; wherein the concentration of the electrolyte is 0.1 mol in the electrolyte /L-10mol/L.
  • the battery has better charge and discharge efficiency, cycle performance, rate performance, high and low temperature performance, and safety performance.
  • the present invention provides a secondary battery negative electrode, wherein a surface of the metal foil in the negative electrode of the secondary battery is provided with a metal oxide film which is electrically insulating and metal ions can migrate.
  • the metal phosphate membrane functions like a solid electrolyte membrane; improves compatibility between the anode and the electrolyte, reduces electrolyte decomposition, improves battery charge and discharge efficiency, battery cycle performance, high and low temperature performance, and safety performance;
  • the preparation method provided by the invention is simple and easy to operate, has low cost, can be industrially produced, and is easy to produce a secondary battery negative electrode with high product consistency, uniform structure and stable performance;
  • the secondary battery provided by the invention has good charging and discharging efficiency, cycle performance, rate performance, high and low temperature performance and safety performance of the battery.
  • Figure 1 is a scanning electron microscope (SEM) image of a conventional aluminum foil
  • Example 2 is an SEM image of a secondary battery negative electrode prepared in Example 1 of the present invention
  • Example 3 is an enlarged view of an SEM image of a secondary battery negative electrode prepared in Example 1 of the present invention.
  • Example 4 is an X-ray energy spectrum (EDS) diagram of the surface of a secondary battery of a secondary battery produced in Example 1 of the present invention.
  • EDS X-ray energy spectrum
  • a first aspect of an embodiment of the present invention provides a secondary battery negative electrode comprising a metal foil and a dense metal phosphate film disposed on a surface of the metal foil, the metal foil simultaneously serving as a negative electrode current collector and a negative electrode active material.
  • the material of the metal foil includes aluminum, copper, iron, tin, zinc, nickel, manganese, lead, antimony, Any one of cadmium and tellurium or an alloy containing at least one of the above metal elements;
  • the material of the metal phosphate film includes aluminum phosphate, copper phosphate, iron phosphate, tin phosphate, zinc phosphate, nickel phosphate, manganese phosphate, One or more of lead phosphate, strontium phosphate, cadmium phosphate, and strontium phosphate.
  • the metal phosphate film may be disposed on one side surface of the metal foil or may be disposed on the entire surface of the metal foil according to a specific application.
  • the metal phosphate film may be disposed only on a surface of the metal foil near the side of the separator; when the secondary battery is a full battery or used in a commercial battery pack, The metal phosphate film may be disposed on a surface of opposite sides of the metal foil or on the entire surface of the metal foil. It can be understood that there is a bare area on the metal foil for soldering the tabs, which is not provided with a metal phosphate film.
  • the secondary battery may be a conventional lithium ion secondary battery, a sodium ion secondary battery, or the like, or may be a dual ion battery.
  • the prior art porous aluminum foil is used as both a negative active material and a current collector, since the aluminum foil has a very high activity, a thin layer of thin aluminum oxide exists on the surface of the aluminum foil, and the lithium ion is first replaced with alumina during charging.
  • the aluminum in the dense aluminum oxide layer on the surface of the aluminum foil is alloyed with lithium ions, and at the same time, the electrolyte contacting the surface of the aluminum foil is decomposed to form a solid electrolyte membrane. Since the volume expansion occurs when the lithium aluminum alloy is formed, the formed solid electrolyte membrane is broken, and the electrolytic solution is again decomposed to form a solid electrolyte membrane to make up for the destruction of the solid electrolyte membrane.
  • the degree of volume expansion of the aluminum foil is continuously increased, and the decomposition of the electrolyte is continuously performed; the volume of the aluminum foil is reduced during discharge, and the solid electrolyte membrane is also damaged to some extent. Therefore, during the charging and discharging process of the battery, especially during the first charging and discharging of the battery, the electrolyte is seriously decomposed, and the charging and discharging efficiency of the battery is relatively low.
  • the metal phosphate film has electronic insulation, and metal ions such as lithium ions may
  • metal ions such as lithium ions may
  • the nature of the conduction, the metal phosphate membrane functions like a solid electrolyte membrane.
  • the secondary battery negative electrode serves both as a negative electrode active material and as a negative electrode current collector.
  • the electrolyte can be prevented from coming into contact with the negative active material to cause decomposition of the electrolytic solution, and the stability of the electrolytic solution can be improved; in the metal ion or the positive active material in the electrolyte
  • the metal ions such as lithium ions, pass through the metal phosphate film layer and form a lithium aluminum alloy with a metal foil material such as aluminum and de-alloy, thereby achieving battery charging and discharging.
  • the metal phosphate acts as a main inorganic component of the solid electrolyte membrane on the surface of the metal foil, and it is advantageous to lower the impedance of the solid electrolyte membrane because of its good lithium guiding property.
  • the metal phosphate film is formed on the surface of the metal foil, it has strong adhesion, forms a good protective effect on the metal foil substrate, improves the compatibility between the battery negative electrode and the electrolyte, improves the charge and discharge efficiency of the battery, and stabilizes the cycle. Sexuality and safety performance.
  • the material of the metal foil includes a metal element or a metal alloy, and specifically may be aluminum, copper, iron, tin, zinc, nickel, manganese, lead, antimony, cadmium, antimony, copper-tin alloy, aluminum tin. Alloys, aluminum-titanium alloys, iron-tin alloys, etc., wherein the proportion of each element in the alloy is conventionally selected.
  • the metal source in the metal phosphate film is the same as the metal element in the metal foil.
  • the metal phosphate film is an aluminum phosphate film.
  • the metal phosphate film is a copper phosphate film.
  • the metal source in the metal phosphate film may be consistent with the metal element in the metal foil.
  • the surface layer of the metal foil has a three-dimensional porous structure, and the porous pore size is from 10 nm to 20 ⁇ m. Alternatively, the porous pore size is from 10 nm to 100 nm. Alternatively, the porous pore size is from 1 ⁇ m to 20 ⁇ m.
  • the surface layer of the metal foil has a three-dimensional porous structure, which increases metal ions such as lithium ion migration channels, and facilitates lithium ion insertion and extraction, thereby improving the rate performance of the battery.
  • the volume expansion of the metal foil negative electrode sheet during charging and discharging of the battery is alleviated, which is advantageous for improving the cycle performance of the battery.
  • the surface layer has a thickness of 1 nm to 10 ⁇ m, and optionally, the surface layer is thick.
  • the degree is from 1 nm to 100 nm, and optionally, the surface layer has a thickness of from 1 ⁇ m to 10 ⁇ m.
  • the thickness ratio of the surface layer to the thickness of the metal foil is 1:10-10000.
  • the thickness ratio of the surface layer to the thickness of the metal foil is 1:10-100.
  • the thickness ratio of the surface layer to the thickness of the metal foil is 1:1000-10000.
  • the metal phosphate film is closely adhered to the surface layer to achieve a metal phosphate film as close as possible to the surface of the surface layer.
  • the metal phosphate film has a thickness of from 1 nm to 3 ⁇ m; alternatively, the metal phosphate film has a thickness of from 1 nm to 100 nm; alternatively, the metal phosphate film has a thickness of from 100 nm to 3 ⁇ m.
  • the ratio of the thickness of the metal phosphate film to the thickness of the metal foil is 1:30-10000.
  • the ratio of the thickness of the metal phosphate film to the thickness of the metal foil is 1:30-100; alternatively, the ratio of the thickness of the metal phosphate film to the thickness of the metal foil is 1:100- 10000.
  • a first aspect of the present invention provides a secondary battery negative electrode, wherein a surface of the metal foil in the negative electrode of the secondary battery is provided with a metal oxide film in which metal ions such as lithium ions can migrate.
  • the metal phosphate membrane functions like a solid electrolyte membrane; improves the compatibility of the anode and the electrolyte, reduces the decomposition of the electrolyte, and improves the charge and discharge efficiency, battery cycle performance, high and low temperature performance, and safety performance of the battery.
  • the present invention is the first surface treatment of a metal foil as a negative electrode active material and also as a current collector material, and a solid electrolyte membrane material is grown, by which the selection range of the electrolyte solvent can be expanded, thereby facilitating the passage of the electrolyte.
  • the choice of solvent is optimized to achieve comprehensive battery performance and expand the application area of the battery.
  • a second aspect of the present invention provides a method for preparing a secondary battery negative electrode, including:
  • the secondary battery negative electrode includes a metal foil and a dense metal phosphate film disposed on the surface of the metal foil, the metal foil simultaneously serving as a negative electrode current collector and a negative electrode active material, and the material of the metal foil includes aluminum, copper, Any one of iron, tin, zinc, nickel, manganese, lead, antimony, cadmium and antimony, or an alloy containing at least one of the above metal elements; the material of the metal phosphate film comprises aluminum phosphate, copper phosphate, phosphoric acid One or more of iron, tin phosphate, zinc phosphate, nickel phosphate, manganese phosphate, lead phosphate, strontium phosphate, cadmium phosphate, and strontium phosphate.
  • the metal phosphate film may be disposed on one side surface of the metal foil or may be disposed on the entire surface of the metal foil according to a specific application.
  • the metal phosphate film may be disposed only on a surface of the metal foil near the side of the separator; when the secondary battery is a full battery or used in a commercial battery pack, The metal phosphate film may be disposed on the surfaces of opposite sides of the metal foil. It can be understood that there is a bare area on the metal foil for soldering the tabs, which is not provided with a metal phosphate film.
  • the chemical reaction between the metal foil raw material and the phosphate-containing solution comprises:
  • the metal foil raw material is immersed in the phosphate-containing solution, and immersed at a temperature of 0 ° C - 80 ° C for 1 minute - 600 minutes; after the immersion is finished, washed with water and dried to obtain a secondary battery negative electrode.
  • the metal foil raw material may be completely immersed in the phosphate-containing solution, and after the reaction, a metal foil having a dense metal phosphate film on the entire surface is obtained, and then the metal foil is separated from the separator.
  • the metal phosphate film on the surface of one side is ground away to obtain a negative electrode provided with a metal phosphate film only on one side of the metal foil; or a protective material is attached to one side of the metal foil raw material before immersion to avoid this.
  • a metal foil on one side is reacted with the phosphate-containing solution, and then the metal foil raw material is immersed in the phosphate-containing solution, so that after the immersion is completed, the metal phosphate can be obtained only on one side surface of the metal foil raw material. Salt film.
  • the metal foil raw material is placed in a solution containing phosphate to carry out a chemical reaction to remove the oxide layer on the surface of the metal foil raw material, and react to form a dense metal phosphate film, thereby improving the charge and discharge efficiency of the battery. And cycle performance; when the metal foil raw material reacts with the phosphate-containing solution, the phosphate-containing solution corrodes the surface of the metal foil raw material to form a three-dimensional porous structure, which facilitates lithium ion insertion and extraction, thereby improving the rate performance of the battery. .
  • the metal phosphate formed by the phosphate and the metal foil raw material is deposited in situ on the surface of the metal foil raw material to finally obtain the secondary battery negative electrode, the secondary battery negative electrode including the metal foil and disposed on the metal A dense metal phosphate film on the foil surface. Due to the corrosion reaction, the thickness of the metal foil may be less than the thickness of the metal foil raw material.
  • the phosphate-containing solution comprises at least one of a phosphoric acid solution, a dihydrogen phosphate solution, a monohydrogen phosphate solution, a pyrophosphoric acid solution, a pyrophosphate solution, a metaphosphoric acid solution, and a metaphosphate solution.
  • the phosphate-containing solution includes phosphoric acid, sodium dihydrogen phosphate, sodium monohydrogen phosphate, pyrophosphoric acid, metaphosphoric acid, sodium pyrophosphate, potassium pyrophosphate, potassium dihydrogen phosphate, potassium monohydrogen phosphate, and partial At least one of sodium phosphate, potassium metaphosphate, copper pyrophosphate, potassium phosphate, tetrametaphosphoric acid, and sodium hexametaphosphate.
  • the mass fraction of the solute in the phosphate-containing solution is 5%-85%; alternatively, the phosphate-containing solution is a solution formed by mixing an oxyacid of phosphorus or a salt thereof with water. .
  • the soaking time is from 30 minutes to 400 minutes, and the soaking temperature is from 10 ° C to 40 ° C.
  • the water washing operation is to wash the metal foil raw material after the reaction two to three times.
  • the drying operation comprises: drying at 40 ° C - 120 ° C for 30 minutes - 600 minutes.
  • the drying operation comprises: drying at 120 ° C - 110 ° C for 120 minutes - 400 minutes.
  • the operation of forming a dense metal phosphate film on the surface of the metal foil raw material by deposition comprises:
  • the secondary battery negative electrode includes a metal foil and is disposed on the surface of the metal foil A dense metal phosphate membrane.
  • a specific fixture in the deposition process, can be used to shield one side surface of the metal foil to ensure that the side surface has no film deposition; after the deposition is completed, metal phosphate can be disposed only on one side surface of the metal foil. Salt film. It is also possible to expose both or all surfaces of the metal foil raw material to the vapor deposition chamber so that a metal phosphate film is provided on both or all surfaces of the metal foil.
  • the preparation method provided by the second aspect of the invention is simple and easy to operate, has low cost, can be industrially produced, and is easy to produce a secondary battery negative electrode with high product consistency, uniform structure and stable performance.
  • a third aspect of the invention provides a secondary battery comprising a positive electrode, an electrolytic solution, a separator, and the negative electrode according to the first aspect.
  • the metal foil of the negative electrode when the metal foil of the negative electrode is provided with a metal phosphate film on only one side surface, when the battery is assembled, one side of the metal foil provided with the metal phosphate film is adjacent to the separator, and is not provided. The other side of the metal phosphate membrane is remote from the membrane.
  • the secondary battery provided by the embodiment of the present invention may be a lithium ion secondary battery, a potassium ion secondary battery, a magnesium ion secondary battery, a sodium ion secondary battery, a calcium ion secondary battery, or a dual ion battery.
  • the cathode active material may be selected from a cathode active material of a conventional sodium ion secondary battery, a cathode active material of a lithium ion secondary battery, a cathode active material of a magnesium ion secondary battery, and a sodium ion secondary battery.
  • the positive electrode active material of the sodium ion secondary battery may be selected from the group consisting of sodium-containing phosphate-based polyanion compounds, tunnel structure compounds, spinel-type oxides, and layer transitions.
  • the positive electrode active material of the lithium ion secondary battery may be selected from lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide or lithium-containing polyanion positive electrode material One or several; specifically, such as lithium iron phosphate, lithium cobaltate, nickel cobalt manganese ternary positive electrode material;
  • the positive electrode active material of the magnesium ion secondary battery includes magnesium metal oxide, metal sulfide or magnesium One or more of the polyanionic compounds.
  • the positive active material in the dual ion battery may be selected from one or more of a carbon material, a sulfide, a nitride, an oxide, and a carbide, and further optionally, the carbon material includes a graphite-based carbon material, One or more of glassy carbon, carbon-carbon composite material, carbon fiber, hard carbon, porous carbon, carbon black, carbon nanotubes, and graphene.
  • the graphite-based carbon material includes one or more of natural graphite, expanded graphite, artificial graphite, mesocarbon microbead graphite, pyrolytic graphite, highly oriented graphite, and three-dimensional graphite sponge.
  • the sulfide is selected from the group consisting of molybdenum disulfide, tungsten disulfide, vanadium disulfide, titanium disulfide, iron disulfide, ferrous sulfide, nickel sulfide, zinc sulfide, cobalt sulfide, manganese sulfide;
  • the nitride is selected from one or more of hexagonal boron nitride and carbon doped hexagonal boron nitride;
  • the oxide is selected from the group consisting of molybdenum trioxide, tungsten trioxide, vanadium pentoxide, vanadium dioxide, titanium dioxide, One or more of zinc oxide, copper oxide, nickel oxide, and manganese oxide;
  • the carbide is selected from one or more of titanium carbide, tantalum carbide, molybdenum carbide, and silicon carbide.
  • the material of the positive electrode current collector includes any one of aluminum, copper, iron, tin, zinc, nickel, titanium, manganese, or an alloy containing at least one of the above metal elements, or a composite containing at least one of the above metal elements. material.
  • the electrolyte includes an electrolyte and a solvent, and the electrolyte includes one or more of a lithium salt, a sodium salt, a potassium salt, a magnesium salt, and a calcium salt; in the electrolyte, the electrolyte
  • the concentration is 0.1 mol / L - 10 mol / L; specifically, the lithium salt may be selected from one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, etc., further optionally lithium hexafluorophosphate;
  • the sodium salt may be selected from chlorine Sodium, sodium fluoride, sodium sulfate, sodium carbonate, sodium phosphate, sodium nitrate, sodium difluorooxalate borate, sodium pyrophosphate, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, trisodium citrate, Sodium metaborate, sodium borate, sodium molybdate, sodium
  • the solvent in the electrolytic solution is not particularly limited as long as the electrolyte can be dissociated into metal ions and anions, and the metal ions and anions can be freely transported.
  • the solvent may be a non-aqueous solvent or a water-based solvent, and the non-aqueous solvent may be an organic solvent or a solvent. a sub-liquid, the organic solvent being selected from one or more of esters, sulfones, ethers, etc., and the optional organic solvent may be selected from the group consisting of propylene carbonate (PC), ethylene carbonate (EC), and diethyl carbonate.
  • PC propylene carbonate
  • EC ethylene carbonate
  • diethyl carbonate diethyl carbonate
  • Ester DEC
  • dimethyl carbonate DMC
  • EMC ethyl methyl carbonate
  • MF methyl formate
  • MA methyl acetate
  • DMA N,N-dimethylacetamide
  • FEC fluorinated Ethylene carbonate
  • MP methyl propionate
  • EP ethyl propionate
  • EA ethyl acetate
  • GBL ⁇ -butyrolactone
  • THF tetrahydrofuran
  • 2-methyltetrahydrofuran 2MeTHF
  • 1,3-dioxocyclopentane DOL
  • 4-methyl-1,3-dioxocyclopentane 4MeDOL
  • dimethoxymethane DM
  • 1,2-dimethoxypropane DMP
  • triethylene glycol dimethyl ether DG
  • dimethyl sulfone MSM
  • DME dimethyl ether
  • ES vinyl sulfite
  • PS propylene sul
  • an additive in order to promote the formation of the negative electrode surface solid electrolyte membrane (SEI) to improve the structural stability, service life and performance of the negative electrode, an additive may be further added to the electrolyte, and the additive may be selected from an ester.
  • SEI negative electrode surface solid electrolyte membrane
  • One or more of a class, a sulfone, an ether, a nitrile, and an olefin such as fluoroethylene carbonate, vinylene carbonate, ethylene carbonate, 1,3-propane sultone, 1 , 4-butane sultone, vinyl sulphate, propylene sulfate, ethylene sulphate, vinyl sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, sulfite Ester, methyl chloroformate, dimethyl sulfoxide, anisole, acetamide, diazabenzene, m-diazabenzene, crown ether 12-crown-4, crown ether 18-crown-6, 4- Fluoroanisole, fluorinated chain ether, difluoromethyl ethylene carbonate, trifluoromethyl ethylene carbonate, chloroethylene carbonate, vinyl bromoacetate, trifluoroethy
  • the separator material is not particularly limited, and an insulating porous polymer film or an inorganic porous film or the like conventionally used in the art, such as a porous polypropylene film, a porous polyethylene film, a porous composite polymer film, and insulation, are used.
  • a fiber paper or a porous ceramic separator or the like is further optionally an insulating fiber separator such as a glass fiber separator.
  • the battery has good charge and discharge efficiency, cycle performance, rate performance, high and low temperature performance, and safety performance.
  • the method for preparing the secondary battery may employ various methods known to those skilled in the art, for example, the following steps may be included:
  • (1) preparing a positive electrode sheet applying a positive electrode slurry to a positive electrode current collector to prepare a positive electrode;
  • the package in the embodiment of the present invention comprises placing the battery core into the battery case, welding the cover plate and the battery case, injecting the electrolyte into the battery case, forming and sealing the battery, and forming and sealing the battery.
  • the present invention is not particularly limited in various techniques known to those skilled in the art.
  • a method for preparing a secondary battery negative electrode comprising:
  • the 50-micron-thick aluminum foil was immersed in a 50% phosphoric acid solution for 60 minutes, and the reacted aluminum foil was washed three times with pure water, and then placed in an oven at a temperature of 80 ° C for 300 minutes to dry. Secondary battery negative electrode. Finally, the treated secondary battery negative electrode is cut into the required negative electrode pieces according to the battery design requirements.
  • FIG. 1 is a scanning electron microscope (SEM) diagram of a conventional aluminum foil
  • FIG. 2 is an SEM image of a secondary battery negative electrode obtained in Example 1 of the present invention
  • FIG. 3 is a SEM of a secondary battery negative electrode obtained in Example 1 of the present invention.
  • this porous structure facilitates the insertion and extraction of lithium ions, thereby improving the rate performance of the battery.
  • a high-capacity, high-performance battery can be prepared by using the negative electrode.
  • EDS X-ray energy spectrum
  • FIG. 4 is an X-ray energy spectrum (EDS) diagram of the surface of a secondary battery of a secondary battery produced in Example 1 of the present invention.
  • EDS X-ray energy spectrum
  • the results showed that there were phosphorus and oxygen on the surface of the aluminum foil, indicating that there is a thin layer of phosphoric acid on the surface of the aluminum foil. Aluminium film layer.
  • the specific test results are shown in Figure 4.
  • the first image represents the distribution of aluminum elements
  • the second image represents the distribution of oxygen elements
  • the third represents the distribution of phosphorus elements.
  • the scale in the figure is 10 ⁇ m.
  • the surface of the negative electrode of the secondary battery produced by the present invention contains phosphorus and oxygen elements, indicating that the present invention produces an aluminum phosphate film on the surface of the aluminum foil.
  • Lithium battery system embodiment 1 Lithium battery system embodiment 1
  • a lithium iron phosphate cathode material having a specific capacity of 140 mAh/g and PVDF and conductive carbon black were coated on an aluminum foil at 95:3:2 as a positive electrode sheet.
  • the processing technology and process control of the positive electrode sheet adopt the current industrialized process technology.
  • the processed secondary battery negative electrode is in a normal manner with the above positive electrode, and the electrolyte is 1 mol/L LiPF6 ethylene carbonate (EC).
  • a mixed solution of dimethyl carbonate (DMC) (volume ratio 1:1), a septum celgard 2400 polypropylene porous membrane assembled into a full battery in an argon-filled glove box to obtain a battery sample C1.
  • DMC dimethyl carbonate
  • septum celgard 2400 polypropylene porous membrane assembled into a full battery in an argon-filled glove box to obtain a battery sample C1.
  • a 50 micron thick aluminum foil was used as the negative electrode.
  • a lithium iron phosphate cathode material having a specific capacity of 140 mAh/g and PVDF and conductive carbon black were coated on an aluminum foil at 95:3:2 as a positive electrode sheet.
  • the processing technology and process control of the positive electrode sheet adopt the current industrialized process technology.
  • EC LiPF6 ethylene carbonate
  • DMC dimethyl carbonate
  • the volume ratio of the two compounds is 1:1.
  • 50% copper pyrophosphate + 30% phosphoric acid means a copper pyrophosphate solution having a mass fraction of 50% and a phosphoric acid solution having a mass fraction of 30% were mixed at a volume ratio of 1:1 to form a phosphate-containing solution.
  • a method for preparing a secondary battery negative electrode comprising:
  • the 50-micron-thick aluminum foil was immersed in a 50% phosphoric acid solution for 60 minutes, and the reacted aluminum foil was washed three times with pure water, and then placed in an oven at a temperature of 80 ° C for 300 minutes to dry. Secondary battery negative electrode. Finally, the treated secondary battery negative electrode is cut into the required negative electrode pieces according to the battery design requirements.
  • Aluminum-graphite dual ion battery system embodiment 1 Aluminum-graphite dual ion battery system embodiment 1
  • a graphite positive electrode material having a specific capacity of 100 mAh/g and PVDF and conductive carbon black were coated on an aluminum foil at 95:3:2 as a positive electrode sheet.
  • the processing technology and process control of the positive electrode sheet adopt the current industrialized process technology, and finally the negative electrode of the secondary battery after the above processing is in a normal manner with the above positive electrode, and the electrolyte is 4 mol/L LiPF6 ethylene carbonate (EC).
  • EC LiPF6 ethylene carbonate
  • EMC ethyl methyl carbonate
  • VC vinylene carbonate
  • diaphragm is celgard 2400 polypropylene porous membrane in argon-filled glove box
  • the battery sample C10 was obtained by assembling into a full battery.
  • a 50 micron thick aluminum foil was used as the negative electrode.
  • a graphite cathode material with a specific capacity of 100 mAh/g and PVDF and conductive carbon black were coated on an aluminum foil as a positive electrode sheet at 95:3:2.
  • the processing technology and process control of the positive electrode sheet were both industrialized and processed.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • VC vinylene carbonate
  • septum celgard 2400 polypropylene porous membrane assembled into a full cell in an argon-filled glove box to obtain a battery sample C00.
  • the volume ratio of the two compounds is 1:1.
  • 50% copper pyrophosphate + 30% phosphoric acid means a copper pyrophosphate solution having a mass fraction of 50% and a phosphoric acid solution having a mass fraction of 30% were mixed at a volume ratio of 1:1 to form a phosphate-containing solution.
  • foils of different materials and graphite are assembled into a battery for formation test, wherein each of the foils is subjected to comparison without phosphoric acid treatment and phosphoric acid treatment, and the specific preparation and test methods can be referred to the examples.
  • the specific steps of 1 can be adjusted to obtain different implementation cases.
  • the specific assembly test results are shown in Table 3.

Abstract

一种二次电池负极及其制备方法和二次电池，该负极包括金属箔和设置在金属箔表面的致密的金属磷酸盐膜，金属箔同时作为负极集流体和负极活性材料，金属箔的材质包括铝、铜、铁、锡、锌、镍、锰、铅、锑、镉和铋中的任意一种，或含有至少一种上述金属元素的合金；金属磷酸盐膜的材质包括磷酸铝、磷酸铜、磷酸铁、磷酸锡、磷酸锌、磷酸镍、磷酸锰、磷酸铅、磷酸锑、磷酸镉和磷酸铋中的一种或多种。金属箔表面设置有一层电子绝缘、锂离子可以迁移的金属磷酸盐膜。金属磷酸盐膜起到了类似固体电解质膜的功能作用；提高了负极和电解液的兼容性，提高了电池的充放电效率、电池循环性能、高低温性能和安全性能。

Description

一种二次电池负极及其制备方法和二次电池 技术领域
本发明涉及二次电池领域，具体涉及一种二次电池负极及其制备方法和二次电池。
背景技术
2016年，中科院深圳先进技术研究院唐永炳研究员及其团队在新型高效电池发面研究取得突破行进展，其研究成果在能源材料顶级期刊《Advanced Energy Materials》上(DOI:10.1002/aenm.201502588)发布了一项全新的铝-石墨双离子电池技术，该技术工作原理有别于现有传统锂电池，且以廉价的石墨作为正极，以铝箔同时作为负极活性材料和集流体；8月份时又在著名材料期刊《Advanced Materials》上(DOI:10.1002/adma.201603735)在线发表了“基于碳包覆多孔铝箔负极的高倍率、长循环、高能量密度双离子电池"。其研究团队利用铝箔作为新型高效电池的负极片，这种新型高效电池体系电池的比能量密度更高、成本更低。因此这种新型高效电池具有重大的应用前景。其研究团队充分认识到利用铝箔作为负极极片时存在的问题，并提出了将铝箔加工成碳包覆多孔铝箔来解决铝箔体积膨胀和电解液兼容性问题。其研究成果显示他们提供的解决方案是可以有效解决铝箔作为负极片存在的问题。
通过在铝箔表面涂覆碳材料的方式，虽然提高了负极与电解液的兼容性，但还存在电解液易分解形成固体电解质膜而消耗电解液的问题。而且其碳涂覆方法还存在加工工艺复杂，加工成本较高的问题。
发明内容
针对于上述问题，本发明提出了一种通过在金属箔表面设置致密的金属磷酸盐膜，可以提高电池的充放电效率、循环性能以及安全性能。
本发明第一方面提供了二次电池负极，包括金属箔和设置在所述金属箔表面的致密的金属磷酸盐膜，所述金属箔同时作为负极集流体和负极活性材料，所述金属箔的材质包括铝、铜、铁、锡、锌、镍、锰、铅、锑、镉和铋中的任意一种，或含有至少一种上述金属元素的合金；所述金属磷酸盐膜的材质包括磷酸铝、磷酸铜、磷酸铁、磷酸锡、磷酸锌、磷酸镍、磷酸锰、磷酸铅、磷酸锑、磷酸镉和磷酸铋中的一种或多种。
其中，所述金属磷酸盐膜中的金属源与所述金属箔中的金属元素相同。
其中，所述金属箔的表层具有三维多孔结构，多孔孔径大小为10nm-20μm。
其中，所述表层的厚度为1nm-10μm，所述表层的厚度与所述金属箔的厚度比为1:10-10000。
其中，所述金属磷酸盐膜的厚度为1nm-3μm，所述金属磷酸盐膜厚度与所述金属箔的厚度比为1:30-10000。
本发明第一方面提供的二次电池负极，所述二次电池负极中金属箔表面设置有一层电子绝缘、金属离子如锂离子可以迁移的金属磷酸盐膜。所述金属磷酸盐膜起到了类似固体电解质膜的功能作用；提高了负极和电解液的兼容性，降低电解液分解，提高了电池的充放电效率、电池循环性能、高低温性能、安全性能。
本发明第二方面提供了一种二次电池负极的制备方法，包括：
提供金属箔原材料，将所述金属箔原材料与含有磷酸根的溶液进行化学反应或者在所述金属箔原材料表面通过沉积的方式形成致密的金属磷酸盐膜，制 得二次电池负极；
所述二次电池负极包括金属箔和设置在所述金属箔表面的致密的金属磷酸盐膜，所述金属箔同时作为负极集流体和负极活性材料，所述金属箔的材质包括铝、铜、铁、锡、锌、镍、锰、铅、锑、镉和铋中的任意一种，或含有至少一种上述金属元素的合金；所述金属磷酸盐膜的材质包括磷酸铝、磷酸铜、磷酸铁、磷酸锡、磷酸锌、磷酸镍、磷酸锰、磷酸铅、磷酸锑、磷酸镉和磷酸铋中的一种或多种。
其中，将所述金属箔原材料与含有磷酸根的溶液进行化学反应的操作包括：
将所述金属箔原材料浸泡在所述含有磷酸根的溶液中，在0℃-80℃温度下浸泡1分钟-600分钟；浸泡结束后，水洗、烘干，制得二次电池负极。
其中，所述含有磷酸根的溶液包括磷酸溶液、磷酸二氢盐溶液、磷酸一氢盐溶液、焦磷酸溶液、焦磷酸盐溶液、偏磷酸溶液和偏磷酸盐溶液中的至少一种；所述含有磷酸根的溶液中的溶质的质量分数为5％-85％。
其中，所述烘干的操作包括：40℃-120℃条件下，烘干30分钟-600分钟。
本发明第二方面提供的制备方法简单易操作，成本较低，可工业化生产，且容易制得产品一致性高、结构均一、性能稳定的二次电池负极。
本发明第三方面提供了一种二次电池，包括正极、电解液、隔膜和如权利要求上述第一方面所述的负极。
其中，所述电解液包括电解质和溶剂，所述电解质包括锂盐、钠盐、钾盐、镁盐和钙盐的一种或多种；所述电解液中，所述电解质的浓度为0.1mol/L-10mol/L。
本发明第三方面提供的二次电池，电池的充放电效率、循环性能、倍率性能、高低温性能以及安全性能较好。
综上，本发明有益效果包括以下几个方面：
1、本发明提供了一种二次电池负极，所述二次电池负极中金属箔表面设置有一层电子绝缘、金属离子可以迁移的金属磷酸盐膜。所述金属磷酸盐膜起到了类似固体电解质膜的功能作用；提高了负极和电解液的兼容性，降低电解液分解，提高了电池的充放电效率、电池循环性能、高低温性能、安全性能；
2、本发明提供的制备方法简单易操作，成本较低，可工业化生产，且容易制得产品一致性高、结构均一、性能稳定的二次电池负极；
3、本发明提供的二次电池，电池的充放电效率、循环性能、倍率性能、高低温性能以及安全性能均较好。
附图说明
图1为普通铝箔的扫描电子显微镜(SEM)图；
图2为本发明实施例1制得的二次电池负极的SEM图；
图3为本发明实施例1制得的二次电池负极的SEM图的放大图；
图4为本发明实施例1制得的二次电池负极表面的X射线能谱(EDS)图。
具体实施方式
以下所述是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本发明的保护范围。
本发明实施方式第一方面提供了一种二次电池负极，包括金属箔和设置在所述金属箔表面的致密的金属磷酸盐膜，所述金属箔同时作为负极集流体和负极活性材料，所述金属箔的材质包括铝、铜、铁、锡、锌、镍、锰、铅、锑、 镉和铋中的任意一种，或含有至少一种上述金属元素的合金；所述金属磷酸盐膜的材质包括磷酸铝、磷酸铜、磷酸铁、磷酸锡、磷酸锌、磷酸镍、磷酸锰、磷酸铅、磷酸锑、磷酸镉和磷酸铋中的一种或多种。
本发明实施例方式中，根据具体的应用情况，所述金属磷酸盐膜可以是设置在所述金属箔的一侧表面，也可以是设置在金属箔的整个表面。当所述二次电池为半电池的时候，所述金属磷酸盐膜可以仅设置在金属箔上靠近隔膜一侧的表面；当所述二次电池为全电池或用于商业电池组的时候，所述金属磷酸盐膜可以设置在金属箔的相对设置的两侧的表面或设置在金属箔的整个表面。可以理解的是，金属箔上会预留有用于焊接极耳的裸露区域，该区域是不会设置金属磷酸盐膜的。
本发明实施例方式中，所述二次电池可以为常规的锂离子二次电池、钠离子二次电池等电池，也可以为双离子电池。
现有技术多孔铝箔既作为负极活性材料又作为集流体时，由于铝箔活性非常高，铝箔表面会存在一层致密的薄层氧化铝，电池在充电时锂离子首先是和氧化铝进行置换反应，铝箔表面的致密氧化铝薄层中的铝再和锂离子进行合金化，与此同时铝箔表面接触的电解液会发生分解形成固体电解质膜。由于锂铝合金化的时候产生体积膨胀，使得形成的固体电解质膜被破坏，电解液再次进行分解形成固体电解质膜弥补之前固体电解质膜被破坏的地方。且随着锂铝合金化在铝箔上不断的进行，铝箔体积膨胀的程度不断加大，电解液的分解也在不断的进行；放电时铝箔体积缩小，固体电解质膜也存在一定程度的破坏。因此电池在充放电过程中，特别是电池首次充放电过程中电解液分解严重，电池的充放电效率比较低。
本发明实施方式中，金属磷酸盐膜具有电子绝缘，金属离子如锂离子可以 导通的性质，该金属磷酸盐膜起到了类似固体电解质膜的功能和作用。所述二次电池负极既作为负极活性材料又作为负极集流体。这种二次电池负极作为负极的时候由于表面存在该电子绝缘层，可以避免电解液与负极活性材料接触而引起电解液分解，提高电解液的稳定性；电解质中的金属离子或者正极活性材料中的金属离子如锂离子通过金属磷酸盐膜层后与金属箔材料如铝形成锂铝合金和去合金化，从而实现电池充放电。而且金属磷酸盐在金属箔表面作为固体电解质膜的主要无机组成部分，由于其具有良好导锂性能，有利降低固体电解质膜的阻抗。此外由于金属磷酸盐膜是在金属箔表面生成的，其具有很强的附着力，对金属箔基体形成良好保护作用，提高了电池负极与电解液兼容性，提高电池的充放电效率、循环稳定性以及安全性能。
本发明实施方式中，所述金属箔的材质包括金属单质或金属合金，具体可以为铝、铜、铁、锡、锌、镍、锰、铅、锑、镉、铋、铜锡合金、铝锡合金、铝钛合金、铁锡合金等，其中，合金中各元素的比例为常规选择。
本发明实施方式中，所述金属磷酸盐膜中的金属源与所述金属箔中的金属元素相同。例如当金属箔为铝箔时，金属磷酸盐膜就为磷酸铝膜。当金属箔为铜箔时，金属磷酸盐膜就为磷酸铜膜。金属磷酸盐膜中的金属源可以与所述金属箔中的金属元素保持一致。
本发明实施方式中，所述金属箔的表层具有三维多孔结构，多孔孔径大小为10nm-20μm。可选地，多孔孔径大小为10nm-100nm。可选地，多孔孔径大小为1μm-20μm。金属箔的表层具有三维多孔结构，增加了金属离子如锂离子迁移通道，有利锂离子嵌入和脱出，从而提高电池的倍率性能。此外，缓解了电池充放电过程中金属箔负极片的体积膨胀，有利提高电池的循环性能。
本发明实施方式中，所述表层的厚度为1nm-10μm，可选地，所述表层的厚 度为1nm-100nm，可选地，所述表层的厚度为1μm-10μm。可选地，所述表层的厚度与所述金属箔的厚度比为1:10-10000。可选地，所述表层的厚度与所述金属箔的厚度比为1:10-100。可选地，所述表层的厚度与所述金属箔的厚度比为1:1000-10000。
本发明实施方式中，所述金属磷酸盐膜与所述表层紧密贴合以尽可能实现金属磷酸盐膜紧密设置在所述表层的表面。
本发明实施方式中，所述金属磷酸盐膜的厚度为1nm-3μm；可选地，金属磷酸盐膜的厚度为1nm-100nm；可选地，金属磷酸盐膜的厚度为100nm-3μm。可选地，所述金属磷酸盐膜厚度与所述金属箔的厚度比为1:30-10000。可选地，所述金属磷酸盐膜厚度与所述金属箔的厚度比为1:30-100；可选地，所述金属磷酸盐膜厚度与所述金属箔的厚度比为1:100-10000。
本发明第一方面提供了一种二次电池负极，所述二次电池负极中金属箔表面设置有一层电子绝缘、金属离子如锂离子可以迁移的金属磷酸盐膜。所述金属磷酸盐膜起到了类似固体电解质膜的功能作用；提高了负极和电解液的兼容性，降低电解液分解，提高了电池的充放电效率、电池循环性能、高低温性能、安全性能。此外，本发明是首次对金属箔作为负极活性材料同时也作为集流体材料时进行表面处理，生长出类固体电解质膜物质，通过这种方式可以扩大电解液溶剂的选择范围，从而有利通过电解液溶剂的选择优化来实现电池综合性能，扩大电池的应用领域。
本发明实施方式第二方面提供了一种二次电池负极的制备方法，包括：
提供金属箔原材料，将所述金属箔原材料与含有磷酸根的溶液进行化学反应或者在所述金属箔原材料表面通过沉积的方式形成致密的金属磷酸盐膜，制得二次电池负极；
所述二次电池负极包括金属箔和设置在所述金属箔表面的致密的金属磷酸盐膜，所述金属箔同时作为负极集流体和负极活性材料，所述金属箔的材质包括铝、铜、铁、锡、锌、镍、锰、铅、锑、镉和铋中的任意一种，或含有至少一种上述金属元素的合金；所述金属磷酸盐膜的材质包括磷酸铝、磷酸铜、磷酸铁、磷酸锡、磷酸锌、磷酸镍、磷酸锰、磷酸铅、磷酸锑、磷酸镉和磷酸铋中的一种或多种。
本发明实施例方式中，根据具体的应用情况，所述金属磷酸盐膜可以是设置在所述金属箔的一侧表面，也可以是设置在金属箔的整个表面。当所述二次电池为半电池的时候，所述金属磷酸盐膜可以仅设置在金属箔上靠近隔膜一侧的表面；当所述二次电池为全电池或用于商业电池组的时候，所述金属磷酸盐膜可以设置在金属箔的相对设置的两侧的表面。可以理解的是，金属箔上会预留有用于焊接极耳的裸露区域，该区域是不会设置金属磷酸盐膜的。
本发明一实施方式中，将所述金属箔原材料与含有磷酸根的溶液进行化学反应的操作包括：
将所述金属箔原材料浸泡在所述含有磷酸根的溶液中，在0℃-80℃温度下浸泡1分钟-600分钟；浸泡结束后，水洗、烘干，制得二次电池负极。
本发明该实施方式中，所述金属箔原材料可以完全浸泡在所述含有磷酸根的溶液中，反应后得到整个表面均设置有致密的金属磷酸盐膜的金属箔，然后将金属箔远离隔膜的一侧的表面上的金属磷酸盐膜打磨掉，得到仅在金属箔一侧表面设置金属磷酸盐膜的负极；或者在浸泡前，将所述金属箔原材料的一侧贴上保护材料以避免这一侧的金属箔与所述含有磷酸根的溶液反应，然后将该金属箔原材料浸泡在所述含有磷酸根的溶液中，这样浸泡结束后，可以只在金属箔原材料的一侧表面得到金属磷酸盐膜。
本发明该实施方式中，将金属箔原材料放置在含有磷酸根的溶液中进行化学反应，以去除金属箔原材料表面的氧化层，反应生成致密的金属磷酸盐膜，从而提高了电池的充放电效率和循环性能；金属箔原材料在与含有磷酸根的溶液反应时，含有磷酸根的溶液会对金属箔原材料表面进行腐蚀形成三维多孔结构，此结构有利锂离子嵌入和脱出，从而提高电池的倍率性能。在腐蚀的同时，磷酸根与金属箔原材料形成的金属磷酸盐原位沉积在金属箔原材料的表面，最终得到所述二次电池负极，所述二次电池负极包括金属箔和设置在所述金属箔表面的致密的金属磷酸盐膜。由于发生了腐蚀反应，金属箔的厚度可能小于金属箔原材料的厚度。
本发明实施方式中，所述含有磷酸根的溶液包括磷酸溶液、磷酸二氢盐溶液、磷酸一氢盐溶液、焦磷酸溶液、焦磷酸盐溶液、偏磷酸溶液和偏磷酸盐溶液中的至少一种；具体地，所述含有磷酸根的溶液包括磷酸、磷酸二氢钠、磷酸一氢钠、焦磷酸、偏磷酸、焦磷酸钠、焦磷酸钾、磷酸二氢钾、磷酸一氢钾、偏磷酸钠、偏磷酸钾、焦磷酸铜、磷酸钾、四偏磷酸和六偏磷酸钠中的至少一种。可选地，所述含有磷酸根的溶液中的溶质的质量分数为5％-85％；可选地，所述含有磷酸根的溶液为磷的含氧酸或其盐与水混合形成的溶液。
本发明实施方式中，所述浸泡时间为30分钟-400分钟，浸泡温度为10℃-40℃。
本发明实施方式中，所述水洗的操作为将反应后的金属箔原材料水洗两到三次。
本发明实施方式中，所述烘干的操作包括：40℃-120℃条件下，烘干30分钟-600分钟。可选地，所述烘干的操作包括：80℃-110℃条件下，烘干120分钟-400分钟。
本发明另一实施方式中，在所述金属箔原材料表面通过沉积的方式形成致密的金属磷酸盐膜的操作包括：
通过化学气相沉积或物理沉积的方式在金属箔原材料表面沉积金属磷酸盐形成致密的金属磷酸盐膜，制得二次电池负极；所述二次电池负极包括金属箔和设置在所述金属箔表面的致密的金属磷酸盐膜。
本发明实施方式中，在沉积过程中，可以先采用特定治具遮蔽金属箔的一侧表面，保证该侧表面无薄膜沉积；沉积结束后，可以得到仅在金属箔的一侧表面设置金属磷酸盐膜。也可以将金属箔原材料两侧表面或所有表面均暴露于气相沉积腔室中，从而在金属箔的两侧表面或所有表面均设置有金属磷酸盐膜。
本发明第二方面提供的制备方法简单易操作，成本较低，可工业化生产，且容易制得产品一致性高、结构均一、性能稳定的二次电池负极。
本发明第三方面提供了一种二次电池，包括正极、电解液、隔膜和如第一方面所述的负极。
本发明实施方式中，当负极中金属箔仅一侧表面设置有金属磷酸盐膜时，组装电池的时候，所述设置有金属磷酸盐膜的金属箔的一侧与隔膜邻近，而未设置有金属磷酸盐膜的另一侧远离隔膜。
本发明实施方式中，本发明实施方式提供的二次电池可以为锂离子二次电池、钾离子二次电池、镁离子二次电池、钠离子二次电池、钙离子二次电池或双离子电池，相应地，所述正极活性材料可以选自常规的钠离子二次电池的正极活性材料、锂离子二次电池的正极活性材料、镁离子二次电池的正极活性材料、钠离子二次电池的正极活性材料、钙离子二次电池的正极活性材料或双离子电池的正极活性材料。可选地，钠离子二次电池的正极活性材料可以选自含钠的磷酸盐类聚阴离子化合物、隧道结构化合物、尖晶石型氧化物、层状过渡 金属氧化物的一种或几种；可选地，锂离子二次电池的正极活性材料可选自锂钴氧化物、锂镍氧化物、锂锰氧化物或含锂的聚阴离子正极材料中的一种或几种；具体如磷酸铁锂、钴酸锂、镍钴锰三元正极材料；可选地，镁离子二次电池的正极活性材料包括镁的金属氧化物、金属硫化物或含镁的聚阴离子化合物的一种或几种。所述双离子电池中的正极活性材料可选自碳材料、硫化物、氮化物、氧化物和碳化物中的一种或多种，进一步可选地，所述碳材料包括石墨类碳材料、玻璃碳、碳碳复合材料、碳纤维、硬碳、多孔炭、炭黑、碳纳米管、石墨烯中的一种或多种。
所述石墨类碳材料包括天然石墨、膨胀石墨、人造石墨、中间相碳微球石墨、热解石墨、高取向石墨、三维石墨海绵中的一种或多种。
所述硫化物选自二硫化钼、二硫化钨、二硫化钒、二硫化钛、二硫化铁、硫化亚铁、硫化镍、硫化锌、硫化钴、硫化锰中的一种或多种；所述氮化物选自六方氮化硼、碳掺杂六方氮化硼中的一种或多种；所述氧化物选自三氧化钼、三氧化钨、五氧化二钒、二氧化钒、二氧化钛、氧化锌、氧化铜、氧化镍、氧化锰中的一种或多种；所述碳化物选自碳化钛、碳化钽、碳化钼、碳化硅中的一种或多种。
所述正极集流体的材质包括铝、铜、铁、锡、锌、镍、钛、锰中的任意一种，或含有至少一种上述金属元素的合金，或含有至少一种上述金属元素的复合材料。
本发明实施方式中，所述电解液包括电解质和溶剂，所述电解质包括锂盐、钠盐、钾盐、镁盐和钙盐的一种或多种；所述电解液中，所述电解质的浓度为0.1mol/L-10mol/L；具体地，锂盐可选自六氟磷酸锂、四氟硼酸锂、高氯酸锂等的一种或多种，进一步可选为六氟磷酸锂；钠盐可选自氯化钠、氟化钠、硫酸 钠、碳酸钠、磷酸钠、硝酸钠、二氟草酸硼酸钠、焦磷酸钠、十二烷基苯磺酸钠、十二烷基硫酸钠、柠檬酸三钠、偏硼酸钠、硼酸钠、钼酸钠、钨酸钠、溴化钠、亚硝酸钠、碘酸钠、碘化钠、硅酸钠、木质素磺酸钠、六氟磷酸钠、草酸钠、铝酸钠、甲基磺酸钠、醋酸钠、重铬酸钠、六氟砷酸钠、四氟硼酸钠、高氯酸钠、三氟甲烷磺酰亚胺钠(NaTFSI)、LiCF3SO3、LiN(SO2CF3)2中的一种或几种，进一步可选为六氟磷酸钠；钾盐可选自氯化钾、氟化钾、硫酸钾、碳酸钾、磷酸钾、硝酸钾、二氟草酸硼酸钾、焦磷酸钾、十二烷基苯磺酸钾、十二烷基硫酸钾、柠檬酸三钾、偏硼酸钾、硼酸钾、钼酸钾、钨酸钾、溴化钾、亚硝酸钾、碘酸钾、碘化钾、硅酸钾、木质素磺酸钾、草酸钾、铝酸钾、甲基磺酸钾、醋酸钾、重铬酸钾、六氟砷酸钾、四氟硼酸钾、高氯酸钾、三氟甲烷磺酰亚胺钾(KTFSI)、KCF3SO3、KN(SO2CF3)2中的一种或多种，进一步可选为六氟磷酸钾；镁盐可以选自有机镁盐或无机镁盐，其中有机镁盐可以选用格氏试剂RMgX，包括但不限于N-甲基苯胺溴化镁、吡咯基溴化镁、乙二胺四乙酸二钠镁(EDTA-Mg)、N,N-二(三甲基硅基)氨基氯化镁、Mg(SnPh3)2、Mg(BR2R'2)2、Mg(AZ3-nRn'R'n”)2型配合物中的一种或几种，其中，R为烷基，X为卤素，A为Al、B、As、P、Sb、Ta或Fe，Z为Cl或Br，R'为芳基，且n'+n”＝n，其中无机镁盐可以选自Mg(ClO4)2、Mg(BF4)2、Mg(PF6)2、MgCl2、MgBr2、MgF2、MgI2、Mg(NO3)2、MgSO4、Mg(SCN)2、MgCrO4、Mg(CF3SO3)2中的一种或几种；钙盐可以选自六氟磷酸钙、四氟硼酸钙、氯化钙、碳酸钙、硫酸钙、硝酸钙、氟化钙、三氟甲磺酸钙、高氯酸钙中的一种或多种。
本发明实施方式中，对电解液中的溶剂没有特别限制，只要可以使电解质离解成金属离子和阴离子，且金属离子和阴离子可以自由迁移即可。具体地，所述溶剂可以为非水基溶剂或水基溶剂，所述非水基溶剂可以为有机溶剂或离 子液体，所述有机溶剂选自酯类、砜类、醚类等的一种或几种，可选的有机溶剂可选自碳酸丙烯酯(PC)、碳酸乙烯酯(EC)、碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸甲乙酯(EMC)、甲酸甲酯(MF)、乙酸甲酯(MA)、N,N-二甲基乙酰胺(DMA)、氟代碳酸乙烯酯(FEC)、丙酸甲酯(MP)、丙酸乙酯(EP)、乙酸乙酯(EA)、γ-丁内酯(GBL)、四氢呋喃(THF)、2-甲基四氢呋喃(2MeTHF)、1,3-二氧环戊烷(DOL)、4-甲基-1,3-二氧环戊烷(4MeDOL)、二甲氧甲烷(DMM)、1,2-二甲氧丙烷(DMP)、三乙二醇二甲醚(DG)、二甲基砜(MSM)、二甲醚(DME)、亚硫酸乙烯酯(ES)、亚硫酸丙烯脂(PS)、亚硫酸二甲脂(DMS)、亚硫酸二乙脂(DES)、冠醚(12-冠-4)中的一种或多种，进一步可选为碳酸甲乙酯；所述离子液体可选自1-乙基-3-甲基咪唑-六氟磷酸盐、1-乙基-3-甲基咪唑-四氟硼酸盐、1-乙基-3-甲基咪唑-双三氟甲基磺酰亚胺盐、1-丙基-3-甲基咪唑-六氟磷酸盐、1-丙基-3-甲基咪唑-四氟硼酸盐、1-丙基-3-甲基咪唑-双三氟甲基磺酰亚胺盐、1-丁基-1-甲基咪唑-六氟磷酸盐、1-丁基-1-甲基咪唑-四氟硼酸盐、1-丁基-1-甲基咪唑-双三氟甲基磺酰亚胺盐、N-丁基-N-甲基吡咯烷-双三氟甲基磺酰亚胺盐、1-丁基-1-甲基吡咯烷-双三氟甲基磺酰亚胺盐、N-甲基-N-丙基吡咯烷-双三氟甲基磺酰亚胺盐、N-甲,丙基哌啶-双三氟甲基磺酰亚胺盐、N-甲,丁基哌啶-双三氟甲基磺酰亚胺盐中的一种或多种。
本发明实施方式中，因为在金属箔材表面生长了一层电子绝缘，金属离子如锂离子导通的金属磷酸盐膜层，使得电池充电放电过程中大大降低了电解液的分解从而使得电池的首充放电效率、安全性能均有效的提高，所以对一些在充放电过程中容易在负极发生还原反应的溶剂而言虽然它们不能单独应用在常规的电池体系上，但可以单独应用在本发明的电池体系中。例如碳酸丙烯酯(PC)无法单独或大比例应用于现有的电池体系，但它可以单独应用在本发明的电池 体系中。
本发明实施方式中，为了促进负极表面固体电解质膜(SEI)的形成，以提高负极的结构稳定性、使用寿命和性能，可以进一步在所述电解液中加入添加剂，所述添加剂可以选自酯类、砜类、醚类、腈类和烯烃类等的一种或多种，如氟代碳酸乙烯酯、碳酸亚乙烯酯、碳酸乙烯亚乙酯、1,3-丙磺酸内酯、1,4-丁磺酸内酯、硫酸乙烯酯、硫酸丙烯酯、硫酸亚乙酯、亚硫酸乙烯酯、亚硫酸丙烯酯、二甲基亚硫酸酯、二乙基亚硫酸酯、亚硫酸亚乙酯、氯代甲酸甲脂、二甲基亚砜、苯甲醚、乙酰胺、二氮杂苯、间二氮杂苯、冠醚12-冠-4、冠醚18-冠-6、4-氟苯甲醚、氟代链状醚、二氟代甲基碳酸乙烯酯、三氟代甲基碳酸乙烯酯、氯代碳酸乙烯酯、溴代碳酸乙烯酯、三氟乙基膦酸、溴代丁内酯、氟代乙酸基乙烷、磷酸酯、亚磷酸酯、磷腈、乙醇胺、碳化二甲胺、环丁基砜、1,3-二氧环戊烷、乙腈、长链烯烃、三氧化二铝、氧化镁、氧化钡、碳酸钠、碳酸钙、二氧化碳、二氧化硫、碳酸锂中的一种或多种，进一步可选为碳酸亚乙烯酯(VC)，所述添加剂在所述电解液中的质量分数为0.1％-20％，进一步可选的为1％-6％。
本发明实施方式中，所述隔膜材料无特别限制，采用本领域常规使用的绝缘的多孔聚合物薄膜或无机多孔薄膜等，如多孔聚丙烯薄膜、多孔聚乙烯薄膜、多孔复合聚合物薄膜、绝缘纤维纸或多孔陶瓷隔膜等，进一步可选地的采用绝缘纤维隔膜，如玻璃纤维隔膜等。
本发明第三方面提供的二次电池，电池的充放电效率、循环性能、倍率性能、高低温性能以及安全性能均较好。
本发明实施方式中，所述二次电池的制备方法可采用本领域技术人员公知的各种方法，例如可以包括以下步骤：
(1)制备正极片：将正极浆料涂覆于正极集流体上制备正极；
(2)制备负极：将上述第一方面所述的二次电池负极作为负极；
(3)封装：将正极、隔膜和负极依次层叠或卷绕制备电池极芯，后封装成电池。
本发明实施方式中的封装包括将电池极芯放入电池壳体中，焊接盖板与电池壳体，在电池壳体中注入电解液、对电池进行化成和封口，化成、封口等技术采用本领域技术人员公知的各种技术，本发明没有特别限制。
下面将结合具体实施例对本发明做进一步详述，应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。实施例及对比例中所采用原料均通过商购得到。
锂电池体系实施例1-38：
一种二次电池负极的制备方法，包括：
将50微米厚度的铝箔浸泡在质量分数为50％磷酸溶液中60分钟，再将反应后的铝箔用纯水清洗三次后放置通烘箱中在80℃温度下进行恒温300分钟烘干，即可得到二次电池负极。最后根据电池设计要求将处理后的二次电池负极裁切成需要的负极极片。
图1为普通铝箔的扫描电子显微镜(SEM)图；图2为本发明实施例1制得的二次电池负极的SEM图；图3为本发明实施例1制得的二次电池负极的SEM图的放大图；如图1、图2、图3所示，经过处理后的铝箔表面呈三维多孔结构，这种结构有利于电池充放电过程中减小铝箔极片体积膨胀，有利提高电池的循环性能。而且这种多孔结构有利锂离子嵌入和脱出，从而提高电池的倍率性能。采用该负极即可制备出高容量高性能的电池。
图4为本发明实施例1制得的二次电池负极表面的X射线能谱(EDS)图。为了 表征磷酸处理后的铝箔是否存在磷酸铝膜层，我们对铝箔表面进行X射线能谱(EDS)分析，分析结果显示铝箔表面有磷、氧元素存在，这说明铝箔表面是存在一层薄的磷酸铝膜层的。具体的测试结果见图4：第一张图代表铝元素的分布图，第二张图代表氧元素的分布图，第三张代表磷元素的分布图，图中的标尺为10μm。从图4中可以看出，本发明制得的二次电池负极表面含有磷和氧元素，说明本发明在铝箔的表面制得了磷酸铝膜。
锂电池体系实施例1
将比容量为140mAh/g的磷酸铁锂正极材料与PVDF、导电炭黑按95:3:2涂覆在铝箔上作为正极片。正极片的加工工艺及过程控制均采用目前产业化的工艺技术，最后将上述加工后的二次电池负极以正常的方式与上述的正极，电解液为1mol/L LiPF6的碳酸乙烯酯(EC)和二甲基碳酸酯(DMC)的混合溶液(体积比为＝1：1)，隔膜为celgard2400聚丙烯多孔膜在充满氩气的手套箱中组装成全电池得到电池样品C1。
锂电池体系对比实施例1
将50微米厚度的铝箔作为负极。将比容量为140mAh/g的磷酸铁锂正极材料与PVDF、导电炭黑按95:3:2涂覆在铝箔上作为正极片。正极片的加工工艺及过程控制均采用目前产业化的工艺技术，最后将加工后的正极片与50微米厚度的铝箔作为负极极片，电解液为1mol/L LiPF6的碳酸乙烯酯(EC)和二甲基碳酸酯(DMC)的混合溶液(体积比为＝1：1)，隔膜为celgard2400聚丙烯多孔膜在充满氩气的手套箱中组装成全电池得到电池样品C0。
其他实施例参照实施例1的具体步骤，对相关参数进行调整即可得到不同的实施案例。具体实施例参数及测试结构见下表1。
表1实施例参数数据及性能测试结果
Figure PCTCN2017078206-appb-000001
Figure PCTCN2017078206-appb-000002
备注：当表格中含有磷酸根的溶液中含有两种化合物时，两种化合物的体积比为1:1。如实施例12中50％焦磷酸铜+30％磷酸表示质量分数为50％的焦磷酸铜溶液和质量分数为30％的磷酸溶液按照体积比为1:1混合形成含有磷酸根的溶液。
根据表1可知，通过在铝箔表面生长一层磷酸铝化合物可以有效的提高电池的充放电效率和循环性能。
铝-石墨双离子电池体系实施例1-38：
一种二次电池负极的制备方法，包括：
将50微米厚度的铝箔浸泡在质量分数为50％磷酸溶液中60分钟，再将反应后的铝箔用纯水清洗三次后放置通烘箱中在80℃温度下进行恒温300分钟烘干，即可得到二次电池负极。最后根据电池设计要求将处理后的二次电池负极裁切成需要的负极极片。
铝-石墨双离子电池体系实施例1
将比容量为100mAh/g的石墨正极材料与PVDF、导电炭黑按95:3:2涂覆在铝箔上作为正极片。正极片的加工工艺及过程控制均采用目前产业化的工艺技术，最后将上述加工后的二次电池负极以正常的方式与上述的正极，电解液为4mol/L LiPF6的碳酸乙烯酯(EC)和碳酸甲乙酯(EMC)的混合溶液(体积比为＝1：1)+2％亚乙烯碳酸酯(VC)，隔膜为celgard2400聚丙烯多孔膜在充满氩气的手套箱 中组装成全电池得到电池样品C10。
对比实施例1
将50微米厚度的铝箔作为负极。将比容量为100mAh/g的石墨正极材料与PVDF、导电炭黑按95:3:2涂覆在铝箔上作为正极片，正极片的加工工艺及过程控制均采用目前产业化的工艺技术，最后将加工后的正极片与铝箔作为负极的极片，电解液为4mol/L LiPF6的碳酸乙烯酯(EC)和碳酸甲乙酯(EMC)的混合溶液(体积比为＝1：1)+2％亚乙烯碳酸酯(VC)，隔膜为celgard2400聚丙烯多孔膜在充满氩气的手套箱中组装成全电池得到电池样品C00。
双离子电池其他实施例参照铝-石墨双离子电池体系实施例1的具体步骤，对相关参数进行调整即可得到不同的实施案例。具体实施例参数及测试结构见下表2。
表2实施例参数数据及性能测试结果
Figure PCTCN2017078206-appb-000003
Figure PCTCN2017078206-appb-000004
备注：当表格中含有磷酸根的溶液中含有两种化合物时，两种化合物的体积比为1:1。如实施例12中50％焦磷酸铜+30％磷酸表示质量分数为50％的焦磷酸铜溶液和质量分数为30％的磷酸溶液按照体积比为1:1混合形成含有磷酸根的溶液。
根据表2可知，通过在铝箔表面生长一层磷酸铝化合物可以有效的提高电池的充放电效率和循环性能。
不同材质的箔材-石墨双离子电池体系实施例1-16
本发明实施例将不同材质的箔材与石墨组装成电池进行形成测试，其中，针对每一种箔材都进行了未进行磷酸处理和进行磷酸处理的对比，具体制备和测试方法可参照实施例1的具体步骤，对相关参数进行调整即可得到不同的实施案例。具体组装测试结果如表3所示。
表3实施例参数数据及性能测试结果
Figure PCTCN2017078206-appb-000005
从表3可以看出，不同材质的金属箔材经过磷酸处理后得到的负极组装电池后电池的首次效率和循环性能均得到有效地提高。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (11)

  1. 一种二次电池负极，其特征在于，包括金属箔和设置在所述金属箔表面的致密的金属磷酸盐膜，所述金属箔同时作为负极集流体和负极活性材料，所述金属箔的材质包括铝、铜、铁、锡、锌、镍、锰、铅、锑、镉和铋中的任意一种，或含有至少一种上述金属元素的合金；所述金属磷酸盐膜的材质包括磷酸铝、磷酸铜、磷酸铁、磷酸锡、磷酸锌、磷酸镍、磷酸锰、磷酸铅、磷酸锑、磷酸镉和磷酸铋中的一种或多种。
  2. 如权利要求1所述的二次电池负极，其特征在于，所述金属磷酸盐膜中的金属源与所述金属箔中的金属元素相同。
  3. 如权利要求1所述的二次电池负极，其特征在于，所述金属箔的表层具有三维多孔结构，多孔孔径大小为10nm-20μm。
  4. 如权利要求3所述的二次电池负极，其特征在于，所述表层的厚度为1nm-10μm，所述表层的厚度与所述金属箔的厚度比为1:10-10000。
  5. 如权利要求1所述的二次电池负极，其特征在于，所述金属磷酸盐膜的厚度为1nm-3μm，所述金属磷酸盐膜厚度与所述金属箔的厚度比为1:30-10000。
  6. 一种二次电池负极的制备方法，其特征在于，包括：
    提供金属箔原材料，将所述金属箔原材料与含有磷酸根的溶液进行化学反 应或者在所述金属箔原材料表面通过沉积的方式形成致密的金属磷酸盐膜，制得二次电池负极；
    所述二次电池负极包括金属箔和设置在所述金属箔表面的致密的金属磷酸盐膜，所述金属箔同时作为负极集流体和负极活性材料，所述金属箔的材质包括铝、铜、铁、锡、锌、镍、锰、铅、锑、镉和铋中的任意一种，或含有至少一种上述金属元素的合金；所述金属磷酸盐膜的材质包括磷酸铝、磷酸铜、磷酸铁、磷酸锡、磷酸锌、磷酸镍、磷酸锰、磷酸铅、磷酸锑、磷酸镉和磷酸铋中的一种或多种。
  7. 如权利要求6所述的二次电池负极的制备方法，其特征在于，将所述金属箔原材料与含有磷酸根的溶液进行化学反应的操作包括：
    将所述金属箔原材料浸泡在所述含有磷酸根的溶液中，在0℃-80℃温度下浸泡1分钟-600分钟；浸泡结束后，水洗、烘干，制得二次电池负极。
  8. 如权利要求7所述的二次电池负极的制备方法，其特征在于，所述含有磷酸根的溶液包括磷酸溶液、磷酸二氢盐溶液、磷酸一氢盐溶液、焦磷酸溶液、焦磷酸盐溶液、偏磷酸溶液和偏磷酸盐溶液中的至少一种；所述含有磷酸根的溶液中的溶质的质量分数为5％-85％。
  9. 如权利要求7所述的二次电池负极的制备方法，其特征在于，所述烘干的操作包括：40℃-120℃条件下，烘干30分钟-600分钟。
  10. 一种二次电池，其特征在于，包括正极、电解液、隔膜和如权利要求 1-5任一项所述的负极。
  11. 如权利要求10所述的二次电池，其特征在于，所述电解液包括电解质和溶剂，所述电解质包括锂盐、钠盐、钾盐、镁盐和钙盐的一种或多种；所述电解液中，所述电解质的浓度为0.1mol/L-10mol/L。
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