WO2017190362A1 - 一种负极材料及其制备方法、含所述负极材料的负极及二次电池 - Google Patents

一种负极材料及其制备方法、含所述负极材料的负极及二次电池 Download PDF

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WO2017190362A1
WO2017190362A1 PCT/CN2016/081344 CN2016081344W WO2017190362A1 WO 2017190362 A1 WO2017190362 A1 WO 2017190362A1 CN 2016081344 W CN2016081344 W CN 2016081344W WO 2017190362 A1 WO2017190362 A1 WO 2017190362A1
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Prior art keywords
negative electrode
electrode material
aluminum foil
carbonate
secondary battery
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PCT/CN2016/081344
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English (en)
French (fr)
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唐永炳
张帆
仝雪峰
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深圳先进技术研究院
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Priority to CN201680085088.9A priority Critical patent/CN109417158A/zh
Priority to PCT/CN2016/081344 priority patent/WO2017190362A1/zh
Publication of WO2017190362A1 publication Critical patent/WO2017190362A1/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

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  • the invention belongs to the field of batteries, and particularly relates to a negative electrode material, a preparation method thereof, a negative electrode including the negative electrode material, and a secondary battery.
  • Lithium-ion batteries have a higher specific capacity and a longer cycle life, making them the preferred choice for power supplies in today's electronics.
  • the core components of a lithium ion battery typically contain a positive electrode, a negative electrode, and an electrolyte.
  • the commercial lithium ion battery uses a transition metal oxide or a polyanionic metal compound as a positive electrode active material, graphite or carbon as a negative electrode active material, and an ester electrolyte as an electrolyte.
  • the positive electrode active material of the commercial lithium ion battery in the prior art contains a transition metal element, which increases the preparation cost of the material, and on the other hand, increases the potential environmental hazard after the battery is discarded; Materials, graphite occupies a large part of the volume and weight in the battery, which limits the battery capacity and energy density of lithium-ion batteries.
  • the research team invented a new type of secondary battery with graphite as the positive active material and aluminum foil as the negative electrode material and current collector.
  • the new battery has less environmental pollution, significantly improved working voltage, and the quality, volume and manufacturing cost of the battery. It is also greatly reduced, so that the energy density of the entire battery is fully improved.
  • the aluminum foil used as the negative electrode has a large volume change during the long-time deintercalation of lithium, and the surface of the aluminum foil is pulverized and detached, and the structural stability thereof is deteriorated, resulting in a new battery cycle using ordinary aluminum foil as a negative electrode material. Poor stability.
  • an object of the present invention is to provide a negative electrode material, a method for preparing the same, a negative electrode including the negative electrode material, and a secondary battery.
  • the present invention provides a negative electrode material comprising a base aluminum foil and a carbon material layer formed on a surface of the base aluminum foil, wherein the base aluminum foil has a porosity of 0 to 85%;
  • the base aluminum foil has a thickness of 10 to 600 ⁇ m, the carbon material layer has a thickness of 2 to 10000 nm, and the carbon layer has a carbon content of 1 to 40% by weight based on the total weight of the negative electrode material.
  • the base aluminum foil is a corroded aluminum foil.
  • the present invention provides a method of preparing a negative electrode material, comprising the steps of:
  • the aluminum foil is immersed in an organic solution in which the organic polymer is dissolved for 0.1 to 24 hours, and after drying, an aluminum foil coated with the organic polymer is obtained, wherein the organic polymer has a mass concentration of 1 to 100 mg/mL;
  • the aluminum foil coated with the organic polymer obtained in the step (1) is heat-treated at 300 to 650 ° C for 1 to 10 hours in an atmosphere of oxygen barrier to obtain the negative electrode material.
  • the organic polymer includes, but is not limited to, polyacrylonitrile, polyvinylidene fluoride, polyacrylic acid, polyurethane, polyvinyl butyral, polytetrafluoroethylene. And one or more of polyurethane.
  • the organic solvent includes, but is not limited to, dimethylformamide, propylene glycol methyl ether, propylene carbonate, ethylene carbonate, dimethyl carbonate, dipropylene carbonate. Ester, ethylene propylene carbonate, vinylene carbonate, ethyl isopropyl carbonate, methylbutyl carbonate, dibutyl carbonate, ethyl butyl carbonate, ethyl methyl carbonate, diethyl carbonate, ⁇ -butyrolactone, N One or several of methyl pyrrolidone.
  • the step (1) is repeated N times, and N is a natural number of not less than 1, and an aluminum foil coated with the organic polymer is obtained.
  • the step (3) may be further included: the etching treatment is performed by using an etchant for 0.1 to 2 hours to prepare the anode material.
  • the anode material according to the first aspect is produced by the method of preparing the anode material according to the second aspect.
  • the present invention provides a negative electrode comprising the negative electrode material according to the first aspect or the negative electrode material obtained by the method for producing the negative electrode material according to the second aspect.
  • the present invention provides a secondary battery including a battery negative electrode, an electrolyte, a separator, and a battery positive electrode, the battery positive electrode including a positive electrode current collector and a positive electrode active material layer, the electrolyte including an electrolyte and a solvent,
  • the negative electrode of the battery includes the negative electrode material described in the first aspect or the negative electrode material obtained by the method for producing a negative electrode material as described in the second aspect.
  • the electrolyte includes one of a lithium salt, a sodium salt or a magnesium salt; and the solvent includes, but is not limited to, one of an ester, a sulfone, an ether, a nitrile organic solvent or an ionic liquid. Or several; the positive electrode active material layer includes a positive electrode active material, and the positive electrode active material has a layered crystal structure.
  • the solvent is preferably ethyl methyl carbonate.
  • the concentration of the electrolyte in the electrolyte is 0.1-10 mol/L.
  • the electrolyte further includes an additive, including but not limited to one or more of an ester, a sulfone, an ether, a nitrile, and an olefin organic additive.
  • an additive including but not limited to one or more of an ester, a sulfone, an ether, a nitrile, and an olefin organic additive.
  • the content of the additive in the electrolyte is 0.1-20% by weight.
  • the additive is vinylene carbonate, and the content of the vinylene carbonate in the electrolyte is 2 wt%.
  • the cathode active material includes one or more of a graphite-based material, a sulfide, a nitride, an oxide, and a carbide having a layered crystal structure.
  • the carbon material layer in the negative electrode material of the embodiment of the present invention may function to maintain the structure of the aluminum foil, thereby making the structure of the negative electrode material stable; and the carbon material layer may also increase the conductivity of the negative electrode material.
  • a method for preparing a negative electrode material according to an embodiment of the present invention by immersing an aluminum foil in an organic polymer solution and then heat-treating, a uniform and tight carbon material layer coated with an aluminum foil anode material can be formed; no hydrocarbon is used in the preparation process.
  • the substances and active additives have simple and controllable preparation process, are safe, reliable, economical and efficient, and have low equipment investment. The raw materials are cheap and easy to obtain, and have cost advantages.
  • the negative electrode material in the secondary battery of the embodiment of the present invention simultaneously serves as a conductive material and as a material which reacts with the cation in the electrolyte
  • the negative electrode of the secondary battery in the prior art generally includes a current collecting current and
  • the active material used for the reaction saves the volume and weight of one part, thus significantly reducing the weight and volume of the secondary battery and increasing the energy density of the secondary battery.
  • the negative electrode material obtained by the method of preparing the negative electrode material according to the first aspect, or the carbon material layer in the negative electrode material is used. Maintaining the function of the aluminum foil structure, so that the anode material maintains structural stability during charging and discharging, thereby improving the cycle performance of the secondary battery in the embodiment of the invention; in addition, the carbon material layer in the anode material can also increase the anode material. The conductivity improves the charge and discharge speed of the secondary battery.
  • FIG. 1 is a schematic structural view of a negative electrode material used in a secondary battery according to an embodiment of the present invention, which includes: a battery negative electrode 1 (aluminum foil 11, carbon material layer 12), an electrolyte 2, and a separator. 3. Battery positive electrode 4 (positive electrode active material 41, current collector 42);
  • an embodiment of the present invention provides a negative electrode material, comprising a base aluminum foil and a carbon material layer formed on a surface of the aluminum foil, wherein the base aluminum foil has a porosity of 0-85%; and the base aluminum foil has a thickness of 10 to 600 ⁇ m, the carbon material layer has a thickness of 2 to 10000 nm, and the carbon material layer has a carbon content of 1 to 40% by weight based on the total weight of the negative electrode material.
  • the base aluminum foil is a corrosion aluminum foil or a non-corrosive aluminum foil.
  • the base aluminum foil is a corroded aluminum foil, and the corroded aluminum foil has a porous structure.
  • the use of corroded aluminum foil can greatly increase the surface area of the aluminum foil without increasing the amount of aluminum or even reducing the weight of the raw material.
  • the corroded aluminum foil has a porosity of 10 to 85%.
  • the carbon material layer functions to maintain the structure of the aluminum foil, so that the structure of the anode material is stable; and the carbon material layer can also increase the conductivity of the anode material. Sex.
  • the present invention provides a method of preparing a negative electrode material, comprising the steps of:
  • the aluminum foil is immersed in an organic solvent in which the organic polymer is dissolved for 0.1 to 24 hours, and dried to obtain an aluminum foil coated with the organic polymer, wherein the organic polymer has a mass concentration of 1 to 100 mg/mL;
  • Step (1) By immersing the aluminum foil in the organic polymer solution, the surface of the aluminum foil can be uniformly adsorbed to the organic polymer.
  • the aluminum foil coated with the organic polymer obtained in the step (1) is heat-treated at 300 to 650 ° C for 0.1 to 24 hours in an inert or reducing gas atmosphere to obtain the negative electrode material.
  • the heat treatment process of the step (2) causes the non-carbon element in the organic polymer to become volatilized, and only carbon (ie, carbonization) remains, which is formed on the surface of the aluminum foil to form a negative electrode material.
  • Heat treatment at 300 ⁇ 650 ° C for 0.1 ⁇ 24h can be completed, is to control the carbonization process by controlling the time, the temperature is higher, the carbonization time is correspondingly shorter; if the temperature is low, the carbonization time is longer.
  • the aluminum foil is a corrosion aluminum foil or a non-corrosive aluminum foil.
  • the aluminum foil is a corroded aluminum foil, and the corroded aluminum foil has a porous structure.
  • the corroded aluminum foil may be obtained by roughing by sandblasting, etching, direct current etching or alternating current etching.
  • the organic polymer includes, but is not limited to, polyacrylonitrile, polyvinylidene fluoride, polyacrylic acid, polyurethane, polyvinyl butyral, polytetrafluoroethylene. And one or more of polyurethane.
  • the organic solvent includes, but is not limited to, dimethylformamide, propylene glycol methyl ether, propylene carbonate, ethylene carbonate, dimethyl carbonate, dipropylene carbonate. Ester, ethylene propylene carbonate, vinylene carbonate, ethyl isopropyl carbonate, methylbutyl carbonate, dibutyl carbonate, ethyl butyl carbonate, ethyl methyl carbonate, diethyl carbonate, ⁇ -butyrolactone, N One or several of methyl pyrrolidone.
  • the step (1) is repeated N times, and N is a natural number of not less than 1, and an aluminum foil coated with the organic polymer is obtained.
  • the step (1) is repeated N times, the aluminum foil can be sufficiently contacted with the organic polymer; the more the number of repetitions of the step (1) The more the content of the organic polymer adsorbed on the surface of the aluminum foil, the thicker the carbon material layer formed on the surface of the aluminum foil after the heat treatment in the step (2), the carbon material layer itself and the carbon material layer and the aluminum foil are tight. More sexual.
  • the N is from 1 to 10, preferably from 5 to 10.
  • the drying treatment is a conventional operation method in the art, and only the solvent is removed, including but not limited to oven drying, natural drying or air drying.
  • the drying treatment in the step (1) is oven drying, and the drying temperature is 50 to 120 °C. Drying at this temperature allows a relatively good drying speed and product effect.
  • the inert or reducing gas includes, but is not limited to, one or more of argon, helium, and hydrogen.
  • step (2) heat treatment in an atmosphere of the inert or reducing gas can effectively prevent the aluminum foil from being oxidized during the heat treatment.
  • the atmosphere of the inert gas is an argon atmosphere or a mixed atmosphere of 5% hydrogen and argon.
  • the oxidation prevention effect is the best.
  • the step (3) may further include: performing an etching treatment using an etchant for 0.1 to 2 hours to obtain the anode material.
  • the etchant includes an acid solution or an alkali solution.
  • the concentration of the etchant is 0.01 to 2 mol/L.
  • the etchant in the step (2), is an acid solution, but the acid solution is not It is limited to one or more of hydrochloric acid, hydrofluoric acid and hydrobromic acid.
  • the etchant is an alkali solution
  • the alkali solution includes, but not limited to, sodium hydroxide, potassium hydroxide and lithium hydroxide.
  • an etching treatment is performed by using an etchant, and a trace amount of aluminum on the surface of the aluminum foil can be etched away, so that between the base aluminum foil and the carbon layer in the negative electrode material obtained by the etchant treatment, A certain gap is left to provide space for the volume effect of the aluminum foil during charging and discharging.
  • the anode material according to the first aspect is produced by the method of preparing the anode material according to the second aspect.
  • the present invention provides a negative electrode comprising the negative electrode material according to the first aspect or the negative electrode material obtained by the method for producing the negative electrode material according to the second aspect.
  • the present invention provides a secondary battery having a structure as shown in FIG. 1 , comprising a battery negative electrode 1 (aluminum foil 11 , carbon layer 12 ), an electrolyte 2 , a separator 3 , and a battery positive electrode 4 , wherein the battery
  • the positive electrode includes a positive electrode current collector 42 and a positive electrode active material layer 41, the positive electrode active material layer includes a positive electrode active material having a layered crystal structure;
  • the electrolyte solution includes an electrolyte and a solvent;
  • the battery negative electrode includes The negative electrode material according to the first aspect or the negative electrode material produced by the method for producing a negative electrode material according to the second aspect.
  • the electrolyte contained in the electrolyte is dissociated into an anion and a cation; when charging the secondary battery of the embodiment of the invention, an external electric field is applied between the anode material and the cathode current collector, and the cation in the electrolyte Deposited on the negative electrode material under the action of an electric field to form an alloy with the aluminum foil in the negative electrode material, and the anion in the electrolyte is embedded in the positive electrode active material under the action of an electric field; when the secondary battery of the embodiment of the invention discharges, the cation and the negative electrode The alloy formed by the aluminum foil in the material is released back into the electrolyte, and the anion embedded in the positive electrode active material is also released back into the electrolyte; thereby achieving reversible charge and discharge.
  • the negative electrode material in the secondary battery of the embodiment of the present invention simultaneously functions as a conductive agent and reacts with a cation in the electrolyte
  • the material generally has a conductive current collector and an active material for reacting compared to the negative electrode of the secondary battery in the prior art, which saves the volume and weight of one component, thereby significantly reducing the weight and volume of the battery. Increase battery energy density.
  • the negative electrode material obtained by the method of preparing the negative electrode material according to the first aspect, or the carbon material layer in the negative electrode material is used to maintain the
  • the function of the aluminum foil structure makes the structure of the anode material stable, thereby improving the cycle rate of the secondary battery in the embodiment of the invention; in addition, the carbon material layer in the anode material can also increase the conductivity of the anode material, thereby improving the secondary battery. Charge and discharge speed.
  • the anode material with corroded aluminum foil can greatly increase the specific surface area of the aluminum foil and increase the contact between the cation and the aluminum in the electrolyte without increasing the amount of aluminum or reducing the weight of the raw material.
  • the area increases the reaction rate and the reaction capacity of the aluminum foil, thereby increasing the battery capacity of the secondary battery in the embodiment of the present invention and further increasing the charge and discharge speed and energy density of the battery.
  • the cathode current collector includes, but is not limited to, one of aluminum, lithium, magnesium, vanadium, copper, iron, tin, zinc, nickel, titanium, manganese, or any one of them. A composite or an alloy of any of them.
  • the positive electrode active material layer comprises 60 to 90% by weight of the positive electrode active material by weight percentage.
  • the positive electrode active material layer comprises, by weight percentage, 1 to 30% by weight of a conductive agent.
  • the positive active material layer comprises, by weight, 1 to 10% by weight of a binder.
  • the positive electrode active material in the positive electrode active layer is also not particularly limited as long as it has a layered crystal structure capable of reversibly extracting or embedding an anion; a binder and a conductive layer in the positive electrode active material layer
  • the agent is also not particularly limited, and it is generally used in the art.
  • the positive active material includes, but is not limited to, graphite having a layered crystal structure.
  • the graphite-based material includes, but is not limited to, natural graphite, artificial graphite or graphite flakes.
  • the sulfide includes, but is not limited to, molybdenum disulfide, tungsten disulfide or vanadium disulfide.
  • the nitride includes, but is not limited to, hexagonal boron nitride or carbon doped hexagonal boron nitride.
  • the oxide includes, but is not limited to, molybdenum trioxide, tungsten trioxide or vanadium pentoxide.
  • the carbide includes, but is not limited to, titanium carbide, tantalum carbide or molybdenum carbide.
  • the cathode active material is a graphite-based material having a layered crystal structure.
  • the conductive agent is one or more of conductive acetylene black, conductive carbon spheres, conductive graphite, carbon nanotubes, and graphene.
  • the binder is one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, styrene butadiene rubber, and polyolefin.
  • the electrolyte is not particularly limited as long as the electrolyte can be dissociated into a cation and an anion.
  • the electrolyte is one of a lithium salt, a sodium salt or a magnesium salt.
  • the lithium salt includes, but is not limited to, lithium bistrifluoromethanesulfonimide, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bisfluorosulfonate, lithium perchlorate, and diethylene glycol.
  • lithium bistrifluoromethanesulfonimide lithium hexafluorophosphate
  • lithium tetrafluoroborate lithium bisfluorosulfonate
  • lithium perchlorate lithium perchlorate
  • diethylene glycol diethylene glycol.
  • the sodium salt includes, but is not limited to, sodium chloride, sodium fluoride, sodium sulfate, sodium carbonate, sodium phosphate, sodium nitrate, sodium difluorooxalate, sodium pyrophosphate, dodecane Sodium benzenesulfonate, sodium lauryl sulfate, trisodium citrate, sodium metaborate, sodium borate, sodium molybdate, sodium tungstate, sodium bromide, sodium nitrite, sodium iodate, sodium iodide, silicon Sodium, Sodium lignosulphonate, sodium hexafluorophosphate, sodium oxalate, sodium aluminate, sodium methanesulfonate, sodium acetate, sodium dichromate, sodium hexafluoroarsenate, sodium tetrafluoroborate, sodium perchlorate, trifluoro One or more of sodium methanesulfonimide.
  • the magnesium salt includes, but is not limited to, magnesium bromide, magnesium chloride, magnesium perchlorate, magnesium format reagent, amino magnesium halide, Mg(BR 2 R' 2 ) 2 (R, R One or more of 'Mc or aryl group', Mg(AX 4-n R n' R' n" ) 2 complex.
  • the concentration of the electrolyte is 0.1 to 10 mol/L.
  • the solvent is not particularly limited as long as the solvent can dissociate the electrolyte into cations and anions, and the cations and anions can freely migrate.
  • the solvent includes, but is not limited to, one or more of an ester, a sulfone, an ether, a nitrile organic solvent, or an ionic liquid.
  • the solvent includes, but is not limited to, one or more of diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, dimethyl sulfone or dimethyl ether.
  • the solvent is ethyl methyl carbonate.
  • the anion in the electrolyte is embedded in the positive electrode active material of the layered crystal structure, and the ethyl carbonate is used as a solvent to prevent the anion in the concentrated electrolyte from being embedded in the positive electrode active material, thereby increasing the secondary battery. Capacity.
  • the electrolyte further includes an additive.
  • the additive is also not particularly limited as long as it can promote the formation of a solid electrolyte membrane (SEI) on the surface of the anode material.
  • SEI solid electrolyte membrane
  • the additives include, but are not limited to, esters, sulfones, ethers, nitriles or alkenes. Hydrocarbon organic additives.
  • the additives include, but are not limited to, vinylene carbonate, ethylene sulfite, propylene sulfite, ethylene sulfate, cyclobutyl sulfone, 1,3-dioxolane Alkane, acetonitrile or long chain olefins.
  • the additive is present in the electrolyte in an amount of from 0.1 to 20% by weight.
  • the additive is vinylene carbonate, and the vinylene carbonate is present in the electrolyte in an amount of 2% by weight.
  • the separator is also not particularly limited, and it is generally used in the art.
  • the separator includes, but is not limited to, an insulating porous polymer film or an inorganic porous film.
  • the separator includes, but is not limited to, a porous polypropylene film, a porous polyethylene film, a porous composite polymer film, a glass fiber paper, or a porous ceramic separator.
  • the membrane is a fiberglass paper.
  • the form of the secondary battery provided by the present invention is not particularly limited, and may be commonly used in the art, such as a button battery, a flat battery, a cylindrical battery, and the like.
  • the present invention provides the use of the negative electrode material according to the second aspect or the method for producing the negative electrode material according to the first aspect, in the preparation of a secondary battery or a negative electrode.
  • the aluminum foil coated with the organic polymer obtained in the step (1) is placed in a tube furnace, sintered in an argon atmosphere at a temperature of 650 ° C for 1 h, and the sintered aluminum foil is diluted with 1 mol/L of hydrochloric acid. Soak for 0.1 h to obtain the final negative electrode material.
  • the steps of the negative electrode material preparation method are the same as those of the first embodiment, except that the materials and processing conditions in the embodiment 1 are replaced by the following Table 1 and Table 2. Shown.
  • the organic polymer solution has the same mass concentration and the same number of immersion repetition times as in Examples 2 and 3.
  • the immersion time of Example 2 is longer than that of Example 3.
  • the carbon layer thickness ratio of Example 2 is as an example.
  • the thickness of 3 indicates that the longer the aluminum foil is immersed, the more organic polymer is adsorbed on the surface of the aluminum foil, and the thicker the carbon layer of the finally obtained negative electrode material.
  • Example 2 In Examples 2 and 8 in which the number of times of soaking was the same and the soaking time was the same, the mass concentration of the organic polymer solution of Example 8 was larger than that of Example 2, and the thickness ratio of the carbon layer of Example 8 in the negative electrode material finally obtained was as an example.
  • the thickness of 2 indicates that the higher the mass concentration of the aluminum foil organic polymer, the more organic polymer adsorbed on the surface of the aluminum foil, and the thicker the carbon layer of the finally obtained negative electrode material.
  • Example 4 In Examples 4 and 5 in which the solution concentration of the organic polymer was the same and the soaking time was the same, the number of times of soaking repetition in Example 5 was larger than that in Example 4.
  • the thickness ratio of the carbon layer of Example 5 was as an example. The thickness of 4 indicates that the more the number of repetitions, the more the organic polymer content adsorbed on the surface of the aluminum foil, and the thicker the carbon layer of the finally obtained negative electrode material.
  • Preparation of battery positive electrode 0.4 g of natural graphite, 0.05 g of conductive acetylene black, 0.05 g of polyvinylidene fluoride was added to 2 mL of nitromethylpyrrolidone solvent, and fully ground to obtain a uniform slurry; then the slurry was uniformly coated on the surface of the aluminum foil. Dry at 80 ° C for 12 h under vacuum. The electrode sheet obtained by drying was cut into a disk having a diameter of 10 mm, compacted with a hydraulic press (10 MPa, 10 s), and placed in a glove box as a battery positive electrode.
  • Formulation of electrolyte 2.87 g of lithium bistrifluoromethanesulfonimide was added to 5 mL of ethyl methyl carbonate in a glove box. Stir well until the lithium bistrifluoromethanesulfonimide is completely dissolved, and prepare a 2 mol/L lithium bistrifluoromethanesulfonimide/ethyl methyl carbonate solution, continue to add 0.1 wt% of vinylene carbonate, and stir. Uniformly used as an electrolyte.
  • the glass fiber paper was cut into discs having a diameter of 16 mm, dried and placed in a glove box for use as a separator.
  • Battery assembly In the argon-protected glove box, the prepared battery positive electrode, the separator, and the battery negative electrode are sequentially closely stacked, and the electrolyte is dripped to completely infiltrate the separator, and then the stacked portion is packaged into the button battery case. Complete battery assembly.
  • the positive electrode current collector is replaced by "aluminum foil” to “aluminum tin alloy”;
  • the "2.87 bistrifluoromethanesulfonimide lithium, 0.1 wt% vinylene carbonate” in the preparation electrolyte is replaced with "2.56 g of lithium di oxalate borate, 20 wt% of acetonitrile”;
  • the battery negative electrode was replaced with a negative electrode material using the negative electrode material preparation method Example 6, and the other steps were the same as in Example 1, to manufacture a battery.
  • Example 8 Compared with the method of Example 1, "0.4 g of natural graphite, 0.05 g of polyvinylidene fluoride" in the preparation of the positive electrode of the battery was replaced with "0.4 g of molybdenum trioxide, 0.05 g of polytetrafluoroethylene”; "5mL ethyl methyl carbonate, 0.1wt% vinylene carbonate” is replaced by "5mL dimethyl sulfone, 20wt% 1,3-dioxolane”; the battery negative electrode is replaced with a negative electrode material preparation method In Example 8, a negative electrode material was obtained, and the other steps were the same as in Example 1, to manufacture a battery.
  • the secondary battery prepared in the above embodiment of the secondary battery preparation method was charged by a constant current of 100 mA/g of the positive electrode active material until its voltage reached 4.8 V, and then discharged at the same current until the voltage reached 3V, measure its battery capacity and energy density, test its cycle stability (in terms of the number of cycles, the number of cycles refers to the number of times the battery is charged and discharged when the battery capacity is attenuated to 85%), as shown in Table 5.
  • Example 5 using the etched aluminum foil and Example 11 using the non-corroded aluminum foil the battery capacity of Example 5 was higher than that of Example 11, indicating that the anode material ratio including the etched aluminum foil was included.
  • the negative electrode material of the non-corrosive aluminum foil is used in the secondary battery to obtain a higher battery capacity;
  • Example 9 In the case where the electrolyte type and concentration are the same, in Example 1 using ethyl methyl carbonate as a solvent and Example 8 using dimethyl sulfone, in Example 9 using dimethyl ether, the battery capacity ratio of Example 1 was carried out.
  • the high of Examples 8 and 9 indicates that ethyl acrylate is used as a solvent, and the secondary battery has a higher battery capacity;
  • Example 3-7 in which the types of additives were different, the number of cycles of Example 3 was more than that of Examples 4-7, indicating that the preferred additive was vinylene carbonate;
  • the additive was vinylene carbonate, and the concentrations were different in Examples 1-3.
  • the concentration of 2 wt% of Example 2 was higher than that of Examples 1 and 3, indicating that the optimum concentration of vinylene carbonate was 2 wt%;
  • Examples 1-3 of the additive were higher in capacity than Example 11 without the additive.
  • the battery examples 1-10 prepared using the negative electrode material provided by the examples of the present invention were higher than the comparative battery Example 1 prepared using ordinary aluminum foil; in the absence of additives
  • the battery example 11 prepared by using the anode material provided by the embodiment of the present invention has a higher number of cycles than the comparative battery example 2 prepared by using the ordinary aluminum foil; indicating that the anode material provided by the embodiment of the invention is used, wherein the carbon layer is used.
  • the function of maintaining the structure of the aluminum foil is such that the structure of the anode material is stabilized, thereby increasing the circulation rate of the secondary battery in the embodiment of the invention.

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Abstract

一种负极材料及其制备方法、含所述负极材料的负极及二次电池，所述负极材料包括基体铝箔及形成于铝箔表面的碳材料层，其中，所述基体铝箔的孔隙率为0～85％；所述基体铝箔的厚度为10～600μm；所述碳材料层的厚度为2～10000nm，所述碳材料层中碳含量为所述电池负极材料总重量的1～40wt％；所述负极材料结构稳定，导电率高。所述负极材料的制备方法制备工艺简单可控，经济高效，能够制备出均匀、紧密性强的碳材料包覆铝箔的负极材料。所述二次电池中使用所述负极材料作为负极，具有电池能量密度高、结构稳定、循环率性能好、充放电速度快的特点。

Description

一种负极材料及其制备方法、含所述负极材料的负极及二次电池 技术领域
本发明属于电池领域，尤其涉及一种负极材料及其制备方法、含所述负极材料的负极及二次电池。
背景技术
随着现代物质生活水平及科技的发展，人们对能源的消耗及需求越来越大，寻找一种新型能源成为当今迫切的需要。锂离子电池因其比容量高，循环寿命长为当今电子产品电源的首选对象。锂离子电池的核心组成部件通常包含正极、负极和电解液。商用的锂离子电池是以过渡金属氧化物或聚阴离子型金属化合物为正极活性材料，以石墨或碳为负极活性材料，酯类电解液为电解液。但现有技术中商用锂离子电池的正极活性材料中包含过渡金属元素，这一方面使得材料的制备成本增加，另一方面也使得电池废弃后对环境的潜在危害加大；以石墨为负极活性材料，石墨在电池中占用了很大一部分的体积和重量，制约了锂离子电池的电池容量及能量密度。
本研究团队发明了一种以石墨为正极活性材料，铝箔同时作为负极材料和集流体的新型二次电池，该新型电池对环境污染小，工作电压显著提高，且电池的质量、体积和制造成本也大幅降低，从而全电池的能量密度得到全面提升。
但是，该新型电池作为负极的铝箔经过长时间脱嵌锂过程中，存在较大的体积变化，使铝箔表面粉化脱落，其结构稳定性变差，导致采用普通铝箔作为负极材料的新型电池循环稳定性较差。
因此，有必要提供一种结构稳定的负极材料及其制备方法，包含所述负极材料的二次电池。
发明内容
针对现有技术的不足，本发明的目的是提供一种负极材料及其制备方法、含所述负极材料的负极及二次电池。
第一方面，本发明提供了一种负极材料，所述负极材料包括基体铝箔及形成于所述基体铝箔表面的碳材料层，其中，所述基体铝箔的孔隙率为0～85％；所述基体铝箔的厚度为10～600μm，所述碳材料层的厚度为2～10000nm，所述碳层中碳含量为所述负极材料总重量的1～40wt％。
优选地，在本发明一实施例中，所述基体铝箔为腐蚀铝箔。
第二方面，本发明提供了一种负极材料的制备方法，包括如下步骤：
(1)将铝箔浸入溶解有有机聚合物的有机溶液0.1～24h，干燥后，获得涂有所述有机聚合物的铝箔，其中，所述有机聚合物的质量浓度为1～100mg/mL；
(2)在隔绝氧气的气氛中，将步骤(1)所得的涂有所述有机聚合物的铝箔在300～650℃下热处理1～10h，制得所述负极材料。
在本发明一实施例中，所述步骤(1)中，所述有机聚合物包括但不限于聚丙烯腈、聚偏氟乙烯、聚丙烯酸、聚氨酯、聚乙烯醇缩丁醛、聚四氟乙烯和聚氨酯中的一种或几种。
在本发明一实施例中，所述步骤(1)中，所述有机溶剂包括但不限于二甲基甲酰胺、丙二醇甲醚、碳酸丙烯脂、碳酸乙烯脂、碳酸二甲脂、碳酸二丙酯、碳酸乙丙酯、碳酸亚乙烯酯、碳酸乙异丙酯、碳酸甲丁酯、碳酸二丁酯、碳酸乙丁酯、碳酸甲乙酯、碳酸二乙酯、γ-丁内酯、N-甲基吡咯烷酮中的一种及几种。
优选地，将所述步骤(1)重复进行N次，N为不小于1的自然数，制得涂有所述机聚合物的铝箔。
进一步地，在所述步骤(2)之后，还可以包括步骤(3)：采用蚀刻剂进行蚀刻处理0.1～2h，制得所述负极材料。
在本发明一实施例中，如第一方面所述的负极材料为采用如第二方面所述的负极材料的制备方法制得。
第三方面，本发明提供了一种负极，包括如第一方面所述的负极材料或采用如第二方面所述的负极材料的制备方法制得的负极材料。
第四方面，本发明提供了一种二次电池，包括电池负极、电解液、隔膜和电池正极，所述电池正极包括正极集流体和正极活性材料层，所述电解液包括电解质和溶剂，所述电池负极包括第一方面所述的负极材料或采用如第二方面所述的负极材料的制备方法制得的负极材料。
本发明实施例中，所述电解质包括锂盐、钠盐或镁盐中的一种；所述溶剂包括但不限于酯类、砜类、醚类、腈类有机溶剂或离子液体中的一种或几种；所述正极活性材料层包括正极活性材料，所述正极活性材料具有层状晶体结构。
本发明实施例中，所述溶剂优选为碳酸甲乙酯。
本发明实施例中，所述电解液中所述电解质的浓度为0.1～10mol/L。
进一步的，本发明一实施例中，所述电解液还包括添加剂，所述添加剂包括但不限于酯类、砜类、醚类、腈类和烯烃类有机添加剂一种或几种。
本发明实施例中，所述电解液中所述添加剂的含量为0.1～20wt％。
优选地，本发明一实施例中，所述添加剂为碳酸亚乙烯酯，所述碳酸亚乙烯酯在所述电解液中的含量为2wt％。
本发明实施例中，所述正极活性材料包括具有层状晶体结构的石墨类材料、硫化物、氮化物、氧化物、碳化物中的一种或几种。
本发明的有益效果在于：
(1)本发明实施例的负极材料中所述碳材料层可以起到维持所述铝箔结构的作用，从而使得负极材料的结构稳定；另外碳材料层还可以增加负极材料的导电性。
(2)本发明实施例的制备负极材料的方法，通过将铝箔浸入有机聚合物溶液中后热处理，可以形成均匀，紧密性强的碳材料层包覆铝箔的负极材料；制备过程中无需使用烃类物质、活性添加剂，制备工艺简单可控，安全可靠、经济高效，设备投资少，原料廉价易得，具有成本优势。
(3)本发明实施例的二次电池中的负极材料同时起导电作用和作为与电解质中阳离子反应的材料，相比于现有技术中二次电池的负极通常包括起导电作用的集流体和用于发生反应的活性材料，节省了一个部件的体积和重量，因此显著降低二次电池的重量和体积，提高二次电池能量密度。
(4)本发明实施例中，采用如第一方面所述的负极材料或采用如第二方面所述的负极材料的制备方法制得的负极材料，所述负极材料中的碳材料层起到维持所述铝箔结构的作用，使得负极材料在充放电的过程中保持结构稳定，从而提高本发明实施例中二次电池的循环性能；另外所述负极材料中的碳材料层还可以增加负极材料的导电性，从而提高二次电池的充放电速度。
附图说明
为了更清楚地说明本申请实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1是本发明实施例提供的图1是本发明实施例提供的负极材料用于二次电池的结构示意图，其中包括：电池负极1(铝箔11、碳材料层12)、电解液2、隔膜3、电池正极4(正极活性材料41、集流体42)；
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。
第一方面，本发明一实施例提供一种负极材料，包括基体铝箔及形成于铝箔表面的碳材料层，其中，所述基体铝箔的孔隙率为0～85％；所述基体铝箔的厚度为10～600μm，所述碳材料层的厚度为2～10000nm，所述碳材料层中碳含量为所述负极材料总重量的1～40wt％。
在本发明一实施例中，所述基体铝箔为腐蚀铝箔或非腐蚀铝箔。
优选地，所述基体铝箔为腐蚀铝箔，所述腐蚀铝箔具有多孔结构。
采用腐蚀铝箔可以在不增加铝用量甚至减少原料重量的前提下极大的提高铝箔的表面积。
具体地，所述腐蚀铝箔的孔隙率为10～85％。
可以理解的是，本发明实施例提供的负极材料，所述碳材料层起到维持所述铝箔结构的作用，从而使得负极材料的结构稳定；另外所述碳材料层还可以增加负极材料的导电性。
第二方面，本发明提供了一种负极材料的制备方法，包括如下步骤：
(1)将铝箔浸入溶解有有机聚合物的有机溶剂0.1～24h，干燥处理，获得涂有所述有机聚合物的铝箔，其中，所述有机聚合物的质量浓度为1～100mg/mL；
步骤(1)通过将铝箔浸入所述有机聚合物溶液中，可以使铝箔表面均匀地吸附有机聚合物。
步骤(1)中铝箔浸入时间越长，铝箔表面吸附的有机聚合物越多，最后获得的负极材料的碳材料层越厚。
步骤(1)中有机聚合物的质量浓度越高，铝箔表面吸附的有机聚合物越多，最后获得的负极材料的碳材料层越厚。
(2)在惰性或还原性气体的气氛中，将步骤(1)所得的涂有所述有机聚合物的铝箔在300～650℃下热处理0.1～24h，制得所述负极材料。
步骤(2)的热处理过程，使得有机聚合物中非碳元素变成气体挥发后只剩下碳(即碳化)，形成于铝箔表面，从而形成负极材料。
步骤(2)中热处理的温度越高，所需热处理的时间越短，热处理的温度越低，所需热处理的时间越长。在300～650℃的温度下热处理0.1～24h可完成，就是通过控制时间，来控制碳化的过程，温度高一些，碳化时间就相应短一些；温度低的话，碳化时间就长一些。
在本发明一实施例中，所述步骤(1)中，所述铝箔为腐蚀铝箔或非腐蚀铝箔。
优选地，所述铝箔为腐蚀铝箔，所述腐蚀铝箔具有多孔结构。所述腐蚀铝箔可以通过采用喷砂、腐蚀、直流电蚀法或交流电蚀法等方法粗化制得。
在本发明一实施例中，所述步骤(1)中，所述有机聚合物包括但不限于聚丙烯腈、聚偏氟乙烯、聚丙烯酸、聚氨酯、聚乙烯醇缩丁醛、聚四氟乙烯和聚氨酯中的一种或几种。
在本发明一实施例中，所述步骤(1)中，所述有机溶剂包括但不限于二甲基甲酰胺、丙二醇甲醚、碳酸丙烯酯、碳酸乙烯酯、碳酸二甲酯、碳酸二丙酯、碳酸乙丙酯、碳酸亚乙烯酯、碳酸乙异丙酯、碳酸甲丁酯、碳酸二丁酯、碳酸乙丁酯、碳酸甲乙酯、碳酸二乙酯、γ-丁内酯、N-甲基吡咯烷酮中的一种及几种。
优选地，将所述步骤(1)重复进行N次，N为不小于1的自然数，获得涂有所述有机聚合物的铝箔。
可以理解的是，在所述负极材料的制备方法中，将所述步骤(1)重复N次，可使所述铝箔与所述有机聚合物充分接触；所述步骤(1)的重复次数越多，所述铝箔表面吸附的有机聚合物含量越多，经所述步骤(2)中的热处理后，形成于铝箔表面的碳材料层越厚，碳材料层本身及碳材料层与铝箔的紧密性更强。
在本发明一实施例中，所述N为1～10，优选为5～10。
在本发明一实施例中，所述步骤(1)中，所述干燥处理为本领域常规操作方法，只需将所述溶剂除去，包括但不限于烘箱烘干、自然晾干或风干。
优选地，所述步骤(1)中的干燥处理为烘箱烘干，烘干温度为50～120℃。在该温度下进行烘箱烘干，可以获得比较良好地干燥速度和产品效果。
在本发明一实施例中，所述步骤(2)中，所述惰性或还原性气体包括但不限于氩气、氦气、氢气中的一种或几种。
可以理解的是，所述步骤(2)中，在所述惰性或还原性气体的气氛中进行热处理，可有效地防止所述铝箔在热处理过程中被氧化。
优选地，所述惰性气体的气氛为氩气或5％氢气和氩气的混气气氛。在这种气氛下，防氧化效果最好。
进一步地，在本发明一实施例中，所述步骤(2)之后，还可以包括步骤(3)：采用蚀刻剂进行蚀刻处理0.1～2h，制得所述负极材料。
所述蚀刻剂包括酸溶液或碱溶液。
在本发明一实施例中，所述步骤(2)中，所述蚀刻剂的浓度为0.01～2mol/L。
在本发明一优选实施例中，所述步骤(2)中，所述蚀刻剂为酸溶液，所述酸溶液但不 限于盐酸、氢氟酸和氢溴酸中的一种或几种。
在本发明一优选实施例中，所述步骤(2)中，所述蚀刻剂为碱溶液，所述碱溶液包括但不限于氢氧化钠、氢氧化钾和氢氧化锂。
可以理解的是，所述蚀刻处理中，采用蚀刻剂进行蚀刻处理，可腐蚀掉所述铝箔表面上微量的铝，这样经蚀刻剂处理获得的负极材料中的基体铝箔和碳层之间将会留有一定缝隙，为所述铝箔在充放电过程中存在的体积效应提供空间。
在本发明一实施例中，如第一方面所述的负极材料为采用如第二方面所述的负极材料的制备方法制得。
第三方面，本发明提供了一种负极，包括第一方面所述的负极材料或采用如第二方面所述的负极材料的制备方法制得的负极材料。
第四方面，本发明提供了一种二次电池，结构如图1所示，包括电池负极1(铝箔11、碳层12)、电解液2、隔膜3和电池正极4，其中，所述电池正极包括正极集流体42和正极活性材料层41，所述正极活性材料层包括正极活性材料，所述正极活性材料具有层状晶体结构；所述电解液包括电解质和溶剂；所述电池负极包括如第一方面所述的负极材料或采用如第二方面所述的负极材料的制备方法制得的负极材料。
在本发明实施例中，包含在电解液中的电解质离解为阴离子和阳离子；对本发明实施例的二次电池充电时，在负极材料和正极集流体之间施加一个外部电场，电解液中的阳离子在电场的作用下沉积到负极材料上与负极材料中的铝箔形成合金，电解液中的阴离子在电场的作用下嵌入到正极活性材料中；本发明实施例的二次电池放电时，阳离子与负极材料中铝箔形成的合金中脱出回到电解液中，嵌入在正极活性材料中的阴离子也脱出回到电解液中；从而实现可逆充放电。
本发明实施例的二次电池中的负极材料同时起导电作用和作为与电解质中阳离子反应 的材料，相比于现有技术中二次电池的负极通常包括起导电作用的集流体和用于发生反应的活性材料，节省了一个部件的体积和重量，因此显著降低电池的重量和体积，提高电池能量密度。
本发明实施例中，采用如第一方面所述的负极材料或采用如第二方面所述的负极材料的制备方法制得的负极材料，所述负极材料中的碳材料层起到维持所述铝箔结构的作用，使得负极材料的结构稳定，从而提高本发明实施例中二次电池的循环率；另外所述负极材料中的碳材料层还可以增加负极材料的导电性，从而提高二次电池的充放电速度。
进一步地，本发明一优选实施例中，采用具有腐蚀铝箔的负极材料，可以在不增加铝用量甚至减少原料重量的前提下极大的提高铝箔的比表面积，增加电解液中阳离子与铝的接触面积，提高铝箔的反应速率及反应容量，从而达到增大本发明实施例中二次电池的电池容量以及进一步提高电池的充放电速度和能量密度。
在本发明一优选实施例中，所述正极集流体包括但不限于铝、锂、镁、钒、铜、铁、锡、锌、镍、钛、锰中的一种或其中任意一种金属的复合物或其中任意一种的合金。
在本发明一优选实施例中，所述正极活性材料层，按重量百分比计，包括60～90wt％正极活性材料。
在本发明一优选实施例中，所述正极活性材料层，按重量百分比计，包括1～30wt％导电剂。
在本发明一优选实施例中，所述正极活性材料层，按重量百分比计，包括1～10wt％粘结剂。
可以理解的是，所述正极活性层中的正极活性材料也没有特别限制，只要其具有层状晶体结构，能够可逆脱出或嵌入阴离子即可；所述正极活性材料层中的粘结剂和导电剂也没有特别限制，本领域现有普通常用的即可。
在本发明一优选实施例中，所述正极活性材料包括但不限于具有层状晶体结构的石墨 类材料、硫化物、氮化物、氧化物、碳化物中的一种或多种。
在本发明一优选实施例中，所述石墨类材料包括但不限于天然石墨、人造石墨或石墨片。
在本发明一优选实施例中，所述硫化物包括但不限于二硫化钼、二硫化钨或二硫化钒。
在本发明一优选实施例中，所述氮化物包括但不限于六方氮化硼或碳掺杂六方氮化硼。
在本发明一优选实施例中，所述氧化物包括但不限于三氧化钼、三氧化钨或五氧化二钒。
在本发明一优选实施例中，所述碳化物包括但不限于碳化钛、碳化钽或碳化钼。
在本发明一优选实施例中，所述正极活性材料为具有层状晶体结构的石墨类材料。
在本发明一优选实施例中，所述导电剂为导电乙炔黑、导电碳球、导电石墨、碳纳米管、石墨烯中的一种或多种。
在本发明一优选实施例中，所述粘结剂为聚偏氟乙烯、聚四氟乙烯、聚乙烯醇、羧甲基纤维素、丁苯橡胶、聚烯烃类中的一种或多种。
在本发明实施例中，所述电解质没有特别限制，只要电解质可以离解成阳离子和阴离子即可。
在本发明一优选实施例中，所述电解质为锂盐、钠盐或镁盐中的一种。
在本发明一优选实施例中，所述锂盐包括但不限于双三氟甲烷磺酰亚胺锂、六氟磷酸锂、四氟硼酸锂、双氟磺酰亚胺锂、高氯酸锂、双乙二酸硼酸锂和二氟草酸硼酸锂中的一种或几种。
在本发明一优选实施例中，所述钠盐包括但不限于氯化钠、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中的一种或几种。
在本发明一优选实施例中，所述镁盐包括但不限于溴化镁、氯化镁、高氯酸镁、镁格式试剂、氨基镁卤化物、Mg(BR2R’2)2(R、R’为烷基或芳基)、Mg(AX4-nRn’R’n”)2络合物中的一种或几种。
在本发明一优选实施例中，在所述电解液中，所述电解质的浓度为0.1～10mol/L。
可以理解的是，所述溶剂没有特别限制，只要溶剂可以使电解质离解成阳离子和阴离子，且阳离子和阴离子可以自由迁移即可。
在本发明一优选实施例中，所述溶剂包括但不限于酯类、砜类、醚类、腈类有机溶剂或离子液体中的一种或几种。
在本发明一优选实施例中，所述溶剂包括但不限于碳酸二乙酯、碳酸二甲酯、碳酸甲乙酯、二甲基砜或二甲醚中的一种或几种。
在本发明一优选实施例中，所述溶剂为碳酸甲乙酯。
电解液中的阴离子嵌入层状晶体结构的正极活性材料中有一定的限度，采用碳酸甲乙酯作为溶剂，能够保进浓剂电解液中的阴离子嵌入到正极活性材料中，从而增加二次电池的容量。
在本发明一实施例中，所述电解液还包括添加剂。
可以理解的是，所述添加剂也没有特别限制，只要其能够促进在负极材料表面形成固体电解质膜(SEI)即可。通过在负极材料表面形成的固体电解质膜(SEI)，可以防止负极材料在充放电时因体积变化所造成的破坏，使负极材料结构和性能稳定，提高负极材料的使用寿命和性能，以提高二次电池的循环性能。
在本发明一优选实施例中，所述添加剂包括但不限于含酯类、砜类、醚类、腈类或烯 烃类有机添加剂。
在本发明一优选实施例中，所述添加剂包括但不限于碳酸亚乙烯酯、亚硫酸亚乙酯、亚硫酸丙烯酯、硫酸亚乙酯、环丁基砜、1，3-二氧环戊烷、乙腈或长链烯烃。
在本发明一优选实施例中，在所述电解液中，所述添加剂的含量为0.1～20wt％。
在本发明一优选实施例中，所述添加剂为碳酸亚乙烯酯，所述碳酸亚乙烯酯在所述电解液中的含量为2wt％。
可以理解的是，所述隔膜也没有特别限制，采用本领域现有普通常用的即可。
在本发明一实施例中，所述隔膜包括但不限于绝缘的多孔聚合物薄膜或无机多孔薄膜。
在本发明一优选实施例中，所述隔膜包括但不限于多孔聚丙烯薄膜、多孔聚乙烯薄膜、多孔复合聚合物薄膜、玻璃纤维纸或多孔陶瓷隔膜。
在本发明一优选实施例中，所述隔膜为玻璃纤维纸。
可以理解的是，本发明所提供的二次电池的形态没有特殊限制，本领域常用的即可，例如扣式电池、平板电池、圆柱电池等形态。
第五方面，本发明还提供了一种如第二方面所述的负极材料或如第一方面所述的负极材料的制备方法在制备二次电池或负极中的应用。
负极材料制备方法实施例1
(1)将5mg的聚丙烯腈溶于5ml的二甲基甲酰胺中，配置成溶解有有机聚合物的有机溶液；将孔隙率为85％的腐蚀性铝箔浸入溶解有有机聚合物的有机溶液0.1h，重复浸入10次，然后在50℃烘箱中烘干，获得涂有所述有机聚合物的铝箔。
(2)将步骤(1)获得的涂有所述有机聚合物的铝箔放入管式炉中，在氩气，温度为650℃下烧结1h，将烧结后的铝箔用1mol/L的稀盐酸浸泡0.1h，得到最终的负极材料。
负极材料制备方法实施例2-11
与负极材料制备方法实施例1的方式相比，负极材料制备方法实施例2-11步骤与实施例1的步骤相同，只是将实施例1中的物料和处理条件替换成如表1和表2所示。
表1负极材料制备方法实施例2-11步骤1中物料及处理条件
Figure PCTCN2016081344-appb-000001
表2负极材料制备方法实施例2-11步骤2中处理条件
Figure PCTCN2016081344-appb-000002
通过对负极材料制备方法实施例1-11所获得的负极材料进行测量，获得以下参数：
表3通过负极材料制备方法实施例1-11获得的负极材料的参数
Figure PCTCN2016081344-appb-000003
Figure PCTCN2016081344-appb-000004
从以上数据可以看出：
有机聚合物溶液的质量浓度相同、浸泡重复次数相同的实施例2和3，实施例2的浸泡时间比实施例3的长，最后获得的负极材料中，实施例2的碳层厚度比实施例3的厚，表明铝箔浸入时间越长，铝箔表面吸附的有机聚合物越多，最后获得的负极材料的碳层越厚。
浸泡重复次数相同、浸泡时间相同的实施例2和8，实施例8的有机聚合物溶液的质量浓度比实施例2的大，最后获得的负极材料中，实施例8的碳层厚度比实施例2的厚，表明铝箔有机聚合物的质量浓度越高，铝箔表面吸附的有机聚合物越多，最后获得的负极材料的碳层越厚。
有机聚合物的溶液质量浓度相同、浸泡时间相同的实施例4和5，实施例5的浸泡重复次数比实施例4的多，最后获得的负极材料中，实施例5的碳层厚度比实施例4的厚，表明重复次数越多，铝箔表面吸附的有机聚合物含量越多，最后获得的负极材料的碳层越厚。
二次电池制备方法实施例1
制备电池正极：将0.4g天然石墨、0.05g导电乙炔黑、0.05g聚偏氟乙烯加入到2mL氮甲基吡咯烷酮溶剂中，充分研磨获得均匀浆料；然后将浆料均匀涂覆于铝箔表面，80℃真空干燥12h。对干燥所得电极片裁切成直径为10mm的圆片，用油压机压实(10MPa，10s)，置于手套箱中作为电池正极备用。
制备电池负极：使用负极材料制备方法实施例1制得负极材料，作为电池负极
配制电解液：在手套箱中称取2.87g双三氟甲烷磺酰亚胺锂加入到5mL碳酸甲乙酯中， 搅拌均匀至双三氟甲烷磺酰亚胺锂完全溶解，配成2mol/L的双三氟甲烷磺酰亚胺锂/碳酸甲乙酯溶液，继续滴加0.1wt％的碳酸亚乙烯酯，搅拌均匀作为电解液备用。
制备隔膜：将玻璃纤维纸裁切成直径为16mm的圆片，烘干后置于手套箱中作为隔膜备用。
电池组装：在氩气保护的手套箱中，将上述制备好的电池正极、隔膜、电池负极依次紧密堆叠，滴加电解液使隔膜完全浸润，然后将上述堆叠部分封装入扣式电池壳体，完成电池组装。
二次电池制备方法实施例2
与实施例1的方式相比，将制备电池正极中的“0.4g天然石墨、0.05g导电乙炔黑”替换成“0.4g人造石墨、0.05g导电碳球”；将配制电解液中的“2.87双三氟甲烷磺酰亚胺锂、0.1wt％的碳酸亚乙烯酯”替换成“3.04g六氟磷酸锂、2wt％的碳酸亚乙烯酯”；将制备隔膜中的“玻璃纤维纸”替换成“多孔聚丙烯隔膜”；电池负极替换成，使用负极材料制备方法实施例2制得负极材料，其他步骤和实施例1中相同，制造电池。
二次电池制备方法实施例3
与实施例1的方式相比，将制备电池正极中的“将0.4g天然石墨、0.05g导电乙炔黑、0.05g聚偏氟乙烯”替换成“将0.4g石墨片、0.05g导电石墨KS6、0.05g聚四氟乙烯”；将配制电解液中的“2.87双三氟甲烷磺酰亚胺锂、0.1wt％的碳酸亚乙烯酯”替换成“3.04g六氟磷酸锂、20wt％的碳酸亚乙烯酯”；将制备隔膜中的“玻璃纤维纸”替换成“多孔陶瓷隔膜”；电池负极替换成，使用负极材料制备方法实施例3制得负极材料，其他步骤和实施例1中相同，制造电池。
二次电池制备方法实施例4
与实施例1的方式相比，将制备电池正极中的“0.05g导电乙炔黑”替换成“0.05g碳纳 米管”；将配制电解液中的“2.87双三氟甲烷磺酰亚胺锂、0.1wt％的碳酸亚乙烯酯”替换成“1.06g高氯酸锂、20wt％的环丁基砜”；将制备隔膜中的“玻璃纤维纸”替换成“复合玻璃纤维隔膜”；电池负极替换成，使用负极材料制备方法实施例4制得负极材料，其他步骤和实施例1中相同，制造电池。
二次电池制备方法实施例5
与实施例1的方式相比，将制备电池正极中的“0.4g天然石墨”替换成“0.9g人造石墨”；将配制电解液中“2.87g双三氟甲烷磺酰亚胺锂、5mL碳酸甲乙酯”替换成“1.40g高氯酸钠、5mL碳酸甲乙酯/聚碳酸酯(碳酸甲乙酯和聚碳酸酯的体积比为1∶1)”；正极集流体由“铝箔”替换成“多孔铝”；电池负极替换成，使用负极材料制备方法实施例5制得负极材料，其他步骤和实施例1中相同，制造电池。
二次电池制备方法实施例6
与实施例1的方式相比，将制备电池正极中的“0.4g天然石墨、0.05g导电乙炔黑、0.05g聚偏氟乙烯”替换成“0.6g六方氮化硼、0.3g石墨烯、0.1g聚乙烯醇”；正极集流体由“铝箔”替换成“铝锡合金”；将配制电解液中的“2.87双三氟甲烷磺酰亚胺锂、0.1wt％的碳酸亚乙烯酯”替换成“2.56g双乙二酸硼酸锂、20wt％的乙腈”；电池负极替换成，使用负极材料制备方法实施例6制得负极材料，其他步骤和实施例1中相同，制造电池。
二次电池制备方法实施例7
与实施例1的方式相比，将制备电池正极中的“0.4g天然石墨、0.05g导电乙炔黑、0.05g聚偏氟乙烯”替换成“0.4g二硫化钼、0.05g石墨烯、0.05g聚四氟乙烯”；正极集流体由“铝箔”替换成“锡箔”；将配制电解液中的“2.87双三氟甲烷磺酰亚胺锂、0.1wt％的碳酸亚乙烯酯”替换成“0.14g双三氟甲烷磺酰亚胺锂、20wt％的硫酸亚乙酯”；电池负极替换成，使用负极材料制备方法实施例7制得负极材料，其他步骤和实施例1中相同，制造电池。
二次电池制备方法实施例8
与实施例1的方式相比，将制备电池正极中的“0.4g天然石墨、0.05g聚偏氟乙烯”替换成“0.4g三氧化钼、0.05g聚四氟乙烯”；将配制电解液中的“5mL碳酸甲乙酯、0.1wt％的碳酸亚乙烯酯”替换成“5mL二甲基砜、20wt％的1，3-二氧环戊烷”；电池负极替换成，使用负极材料制备方法实施例8制得负极材料，其他步骤和实施例1中相同，制造电池。
二次电池制备方法实施例9
与实施例1的方式相比，将制备电池正极中的“0.4g天然石墨、0.05g聚偏氟乙烯”替换成“0.4g碳化钛、0.05g羟甲基纤维素”；将配制电解液中的“5mL碳酸甲乙酯、0.1wt％的碳酸亚乙烯酯”替换成“5mL二甲基醚、2wt％的碳酸亚乙烯酯”；电池负极替换成，使用负极材料制备方法实施例9制得负极材料，其他步骤和实施例1中相同，制造电池。
二次电池制备方法实施例10
与实施例1的方式相比，将制备电池正极中的“0.4g天然石墨、0.05g聚偏氟乙烯”替换成“0.4g人造石墨、0.05g羟甲基纤维素”；将配制电解液中的“5mL碳酸甲乙酯、2.87g双三氟甲烷磺酰亚胺锂、0.1wt％的碳酸亚乙烯酯”替换成“5mL四氢呋喃、0.67g乙基溴化镁、2wt％的碳酸亚乙烯酯”；将制备隔膜中的“玻璃纤维纸”替换成“多孔陶瓷隔膜”；电池负极替换成，使用负极材料制备方法实施例10制得负极材料，其他步骤和实施例1中相同，制造电池。
二次电池制备方法实施例11
与实施例1的方式相比，将配制电解液中“2.87g双三氟甲烷磺酰亚胺锂、5mL碳酸甲乙酯”替换成“1.40g高氯酸钠、5mL碳酸甲乙酯/聚碳酸酯(碳酸甲乙酯和聚碳酸酯的体积比为1∶1)”，在配制电解液时不加添加剂；电池负极替换成，使用负极材料制备方法实施例11制得负极材料，其他步骤和实施例1中相同，制造电池。
二次电池制备方法对比实施例1
与实施例1的方法相比，将配制电解液中“2.87g双三氟甲烷磺酰亚胺锂”替换成“1.52g六氟磷酸锂”；电池负极替换成铝箔，其他步骤和实施例1中相同，制造电池。
二次电池制备方法对比实施例2
与对比实施例1的方法相比，没有滴加碳酸亚乙烯酯，即没有使用添加剂，其他步骤和对比实施例1中相同，制造电池。
电池的性能测试
充电-放电试验：将上述二次电池制备方法实施例中制备的二次电池通过100mA/g正极活性材料的恒定电流充电，直至其电压达到4.8V，然后以相同的电流放电，直至其电压达到3V，测量其电池容量及能量密度，测试其循环稳定性(以循环圈数表示，循环圈数是指电池容量衰减至85％时电池所充放电次数)，如表5所示。
表5电池的性能测试结果
Figure PCTCN2016081344-appb-000005
Figure PCTCN2016081344-appb-000006
从以上测试结果可以看出：
在电解质种类和浓度相同的情况下，使用腐蚀铝箔的实施例5与使用非腐蚀铝箔的实施例11中，实施例5的电池容量比实施例11的高，表明包括腐蚀铝箔的负极材料比包括非腐蚀铝箔的负极材料用于二次电池中获得的电池容量更高；
在电解质种类和浓度相同的情况下，使用碳酸甲乙酯作为溶剂的实施例1与使用二甲基砜的实施例8、使用二甲醚的实施例9中，实施例1的电池容量比实施例8、9的高，表明采用碳酸甲乙酯作为溶剂，二次电池获得的电池容量更高；
添加剂种类不一样的实施例3-7，实施例3的循环圈数多于实施例4-7，表明优选的添加剂为碳酸亚乙烯酯；
添加剂为碳酸亚乙烯酯，浓度不同的实施例1-3，浓度为2wt％的实施例2比实施例1、3的循环圈数多，表明碳酸亚乙烯酯的最佳浓度是2wt％；有添加剂的实施例1-3要比没有添加剂的实施例11的容量高。
在都使用有添加剂的情况下，使用本发明实施例提供的负极材料制备的电池实施例1-10比使用普通铝箔制备的对比电池实施例1的循环圈数都要高；在没有使用添加剂的情况下，使用本发明实施例提供的负极材料制备的电池实施例11比使用普通铝箔制备的对比电池实施例2的循环圈数要高；表明使用本发明实施例提供的负极材料，其中碳层起到维持所述铝箔结构的作用，使得负极材料的结构稳定，从而提高本发明实施例中二次电池的循环率。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (16)

  1. 一种负极材料，其特征在于，所述负极材料包括基体铝箔及形成于所述基体铝箔表面的碳材料层，其中，所述基体铝箔的孔隙率为0～85％；所述基体铝箔的厚度为10～600μm，所述碳材料层的厚度为2～10000nm，所述碳材料层中碳含量为所述负极材料总重量的1～40wt％。
  2. 一种如权利要求1所述的负极材料，其特征在于，所述基体铝箔为腐蚀铝箔。
  3. 一种负极材料的制备方法，其特征在于，包括如下步骤：
    (1)将铝箔浸入溶解有有机聚合物的有机溶液0.1～24h，干燥后，获得涂有所述有机聚合物的铝箔，其中，所述有机聚合物的质量浓度为1～100mg/mL；
    (2)在隔绝氧气的气氛中，将步骤(1)所得的涂有所述有机聚合物的铝箔在300～650℃下热处理1～10h，制得所述负极材料。
  4. 如权利要求3所述的负极材料的制备方法，其特征在于，所述步骤(1)中，所述有机聚合物包括聚丙烯腈、聚偏氟乙烯、聚丙烯酸、聚氨酯、聚乙烯醇缩丁醛、聚四氟乙烯和聚氨酯中的一种或几种；所述有机溶剂包括二甲基甲酰胺、丙二醇甲醚、碳酸丙烯脂、碳酸乙烯脂、碳酸二甲脂、碳酸二丙酯、碳酸乙丙酯、碳酸亚乙烯酯、碳酸乙异丙酯、碳酸甲丁酯、碳酸二丁酯、碳酸乙丁酯、碳酸甲乙酯、碳酸二乙酯、γ-丁内酯、N-甲基吡咯烷酮中的一种及几种。
  5. 如权利要求3所述的负极材料的制备方法，其特征在于，将所述步骤(1)重复进行N次，N为不小于1的自然数，获得涂所述有机聚合物的铝箔。
  6. 如权利要求3所述的负极材料的制备方法，其特征在于，在所述步骤(2)之后，还可以包括步骤(3)：采用蚀刻剂进行蚀刻处理0.1～2h，制得所述负极材料。
  7. 一种负极材料，其特征在于采用如权利要求3-6中任一所述的负极材料的制备方法制得。
  8. 一种负极，其特征在于，包括如权利要求3-6任一所述的制备方法制得的负极材料或采用如权利要求1-2中任一所述的负极材料。
  9. 一种二次电池，其特征在于，包括电池负极、电解液、隔膜和电池正极，所述电池正极包括正极集流体和正极活性材料层，所述正极活性材料层包括正极活性材料，所述正极活性材料具有层状晶体结构；所述电解液包括电解质和溶剂，其特征在于，所述电池负极包括如权利要求1-2任一所述的负极材料或采用如权利要求3-6中任一所述的负极材料的制备方法制得的负极材料。
  10. 如权利要求9所述的二次电池，其特征在于，所述电解质包括锂盐、钠盐或镁盐中的一种；所述溶剂包括酯类、砜类、醚类、腈类有机溶剂或离子液体中的一种或几种。
  11. 如权利要求10所述的二次电池，其特征在于，所述溶剂为碳酸甲乙酯。
  12. 如权利要求10所述的二次电池，其特征在于，在所述电解液中，所述电解质的浓度为0.1～10mol/L。
  13. 如权利要求9所述的二次电池，其特征在于，所述电解液还包括添加剂，所述添加剂包括含酯类、砜类、醚类、腈类和烯烃类有机添加剂一种或几种。
  14. 如权利要求13所述的二次电池，其特征在于，所述电解液中，所述添加剂的含量为0.1～20wt％。
  15. 如权利要求13所述的二次电池，其特征在于，所述添加剂为碳酸亚乙烯酯，所述碳酸亚乙烯酯在所述电解液中的含量为2wt％。
  16. 如权利要求9所述的二次电池，其特征在于，所述正极活性材料包括具有层状晶体结构的石墨类材料、硫化物、氮化物、氧化物、碳化物中的一种或几种。
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