WO2021068575A1 - 一种金属负极电池的改性隔膜、制备方法及应用 - Google Patents

一种金属负极电池的改性隔膜、制备方法及应用 Download PDF

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WO2021068575A1
WO2021068575A1 PCT/CN2020/100430 CN2020100430W WO2021068575A1 WO 2021068575 A1 WO2021068575 A1 WO 2021068575A1 CN 2020100430 W CN2020100430 W CN 2020100430W WO 2021068575 A1 WO2021068575 A1 WO 2021068575A1
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separator
battery
film
modified
metal
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PCT/CN2020/100430
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English (en)
French (fr)
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唐永炳
黎重重
周小龙
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深圳先进技术研究院
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Publication of WO2021068575A1 publication Critical patent/WO2021068575A1/zh

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  • the invention relates to the technical field of energy storage devices, in particular to a modified diaphragm of a metal negative electrode battery, a preparation method and an application.
  • Lithium metal batteries include positive current collectors, positive electrodes, separators, electrolytes, and negative electrodes; lithium metal batteries can greatly improve battery performance, enhance battery power endurance, greatly improve the economic benefits of power storage, and promote the upgrading and transformation of consumer electronic products. It is of great significance to human life.
  • the membrane used is selected from woven membranes, non-woven membranes (non-woven fabrics), microporous membranes, composite membranes, membrane paper, laminated membranes, polyolefin membranes, etc.
  • the lithium metal negative electrode is prone to generate dendrites during the continuous deposition-stripping process, which will pierce the diaphragm, causing the battery to short-circuit and fail;
  • the metal lithium and the electrolyte are The solid electrolyte layer (SEI film) formed by the interface reaction continues to thicken over time, the interface impedance continues to increase, the Coulomb efficiency decreases, and the battery capacity decreases;
  • SEI film Solid electrolyte layer
  • the SEI film Unstable.
  • the deposition-stripping process it continuously generates-ruptures-regenerates, consuming metal lithium and electrolyte.
  • the purpose of the present invention is to provide a modified separator for a metal negative electrode battery, a preparation method and an application, aiming to solve the problem that the battery separator is easily pierced by metal dendrites in the prior art and affects the safety and stability of the battery.
  • a modified diaphragm for a metal negative electrode battery includes a porous polyolefin diaphragm and a film deposited at least on the surface of the porous polyolefin diaphragm adjacent to the negative electrode material, wherein the film includes a diamond-like carbon film.
  • a method for preparing a modified separator of a metal negative electrode battery comprising a porous polyolefin separator and a thin film deposited at least on the surface of the porous polyolefin separator adjacent to the negative electrode material, wherein the preparation of the thin film
  • the method is selected from any one of magnetron sputtering method, plasma chemical vapor deposition method, ion beam assisted deposition method, pulsed laser deposition method or filtered cathode vacuum arc deposition method.
  • a secondary battery comprising a positive electrode current collector, a positive electrode active material, a separator, an electrolyte, and a metal negative electrode; wherein the separator is the modified separator of the aforementioned metal negative electrode battery or is composed of the aforementioned metal negative electrode
  • the modified diaphragm prepared by the method for preparing the modified diaphragm of the battery.
  • the modified separator for a metal negative electrode battery provided by the present invention includes a porous polyolefin separator and a thin film deposited at least on the surface of the porous polyolefin separator adjacent to the negative electrode material, wherein the thin film includes a diamond-like carbon film .
  • the porous polyolefin membrane is modified by a thin film, and the thin film includes a diamond-like carbon film, which has the following advantages:
  • the diamond-like carbon film has strong chemical inertness, which improves the oxidation resistance and corrosion resistance of the diaphragm; the diamond-like carbon film has strong adhesion, can uniformly deposit on the surface of the diaphragm, and keep the modification effect even and flat; the diamond-like carbon film has The higher strength enhances the strength of the diaphragm, can hinder the growth of metal dendrites, change the growth direction of dendrites, and make them grow laterally, avoiding metal dendrites from piercing the diaphragm, and effectively avoiding short-circuit failure of the battery due to damage to the diaphragm.
  • the safety of the battery is improved, and at the same time, it can guide the uniform deposition of the negative electrode metal, improve the stability of the metal negative electrode, and greatly enhance the cycle stability of the battery.
  • the present invention also provides a method for preparing a modified separator of a metal negative electrode battery.
  • the modified separator includes a porous polyolefin separator and a thin film deposited at least on the surface of the porous polyolefin separator adjacent to the negative electrode material, wherein the thin film
  • the preparation method is selected from any one of magnetron sputtering method, plasma chemical vapor deposition method, ion beam assisted deposition method, pulsed laser deposition method or filtered cathode vacuum arc deposition method.
  • the preparation method of the modified diaphragm of the battery is simple, convenient to operate, high in safety, low in cost, and will not cause damage to the diaphragm material itself. At the same time, it can ensure that the modified diaphragm of the prepared battery is flat and uniform, which is beneficial to subsequent reactions.
  • the present invention also provides a secondary battery, which includes a positive electrode current collector, a positive electrode, a separator, an electrolyte, and a metal negative electrode; wherein, the separator is the modified separator of the above-mentioned metal negative battery or is composed of the above-mentioned metal negative electrode.
  • the modified diaphragm prepared by the method for preparing the modified diaphragm of the battery. Using the above modified diaphragm as the diaphragm of the metal negative electrode battery can effectively hinder the growth of metal dendrites, avoid metal dendrites from piercing the diaphragm, improve the safety of the metal negative battery, and improve the cycle stability and high rate of the energy storage device. It has better performance.
  • FIG. 1 is a modified diaphragm structure of a metal negative electrode battery provided by an embodiment of the present invention.
  • Fig. 2 is a schematic structural diagram of a secondary battery provided by an embodiment of the present invention.
  • Example 3 is a battery performance analysis diagram of the secondary battery prepared by the method in Example 1 and the secondary battery prepared by the method in Example 6 of the present invention.
  • first and second are only used for description purposes, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features. Therefore, the features defined with “first” and “second” may explicitly or implicitly include one or more of these features.
  • “plurality” means two or more than two, unless otherwise specifically defined.
  • An example of the present invention provides a modified separator of a metal negative battery.
  • the structure of the modified separator of the metal negative battery is shown in FIG. 1.
  • the modified separator includes a porous polyolefin separator 1 and at least deposited on the porous polyolefin.
  • the olefin separator 1 is adjacent to the thin film 2 on the surface of the negative electrode material.
  • the modified membrane includes a porous polyolefin membrane and a film deposited on at least two surfaces of the porous polyolefin membrane.
  • the film includes a diamond-like carbon film.
  • the porous polyolefin diaphragm is modified with a thin film, the thin film includes a diamond-like carbon film, which has strong chemical inertness, improves the oxidation resistance and corrosion resistance of the diaphragm; has strong adhesion and can be uniform It is deposited on the surface of the diaphragm to keep the modification effect even and flat; the diamond-like carbon film has high strength, enhances the strength of the diaphragm, can hinder the growth of metal dendrites, change the growth direction of dendrites, and make them grow laterally, avoiding metal Dendrites pierce the diaphragm, effectively avoiding short-circuit failure of the battery due to damage to the diaphragm, improving the safety of the battery, and guiding the uniform deposition of the negative electrode metal, stabilizing the stability of the metal negative electrode, and further enhancing the cycle stability of the battery.
  • diamond-like carbon is an amorphous carbon material with high hardness, high resistivity, good optical properties, and strong chemical inertness.
  • Diamond-like carbon mainly contains two kinds of hybrid bonds, sp 2 and sp 3 , and there are a certain number of CH bonds in hydrogen-containing diamond-like carbon films.
  • the diamond-like carbon film is selected from at least one of an amorphous carbon film, a tetrahedral amorphous carbon film, a polymer-like amorphous carbon film, a diamond-like carbon film, and a graphitic carbon film.
  • the diamond-like carbon film in the element-doped diamond-like carbon film is selected from amorphous carbon film or tetrahedral amorphous carbon film, wherein the amorphous carbon film is mainly composed of sp 3 and sp 2 bonded carbon
  • the tetrahedral amorphous carbon film is composed of a three-dimensional network of intermixed atoms.
  • the tetrahedral amorphous carbon film is mainly composed of more than 80% sp 3 bonded carbon atoms as the skeleton.
  • the diamond-like carbon film is a non-hydrogen tetrahedral (ta-C) film.
  • the thin film is selected from at least one of a thin film formed of a diamond-like material and an element-doped diamond-like carbon film.
  • the film is an element-doped diamond-like carbon film, and the element-doped diamond-like carbon film is used as the film material, which can further improve the conductivity, ion conductivity, and toughness of the battery, and is beneficial to improve the film
  • the combination performance with the separator can further improve the stability and reduce the resistivity, and improve the cycle performance and rate performance of the battery.
  • the doping element is a metal element or a non-metal element.
  • a diamond-like film with doped elements is used as the film deposited on the porous polyolefin separator.
  • the doping element is a metal element, the ion conductivity and toughness of the battery can be further improved, which is beneficial to improve the film and the diaphragm. Combined with performance, improve the cycle performance and rate performance of the battery.
  • the doping element is selected from any one of aluminum element, titanium element, tin element, zinc element, copper element and the like.
  • an aluminum-doped diamond-like carbon film is prepared, and the aluminum-doped diamond-like carbon film is used as the film to be deposited on the adjacent negative electrode of the porous polyolefin separator.
  • the surface of the material is modified to improve the ion conductivity and thermal conductivity of the battery.
  • the lithium deposition process can also form an aluminum-lithium alloy with aluminum to reduce the generation of lithium dendrites and improve the cycle performance and rate performance of the battery.
  • a titanium-doped diamond-like carbon film is prepared, and the titanium-doped diamond-like carbon film is used as the film to be deposited adjacent to the porous polyolefin membrane
  • the surface of the negative electrode material has a modified separator, which improves the toughness of the modified separator, improves the bonding performance of the film and the separator, and significantly enhances its adhesion.
  • a diamond-like film with doped elements is used as the film deposited on the porous polyolefin separator.
  • the doped element is a non-metallic element, it can further improve the stability and reduce the resistivity, and improve the cycle performance and rate performance of the battery.
  • the non-metal element is selected from any one of fluorine element, nitrogen element, hydrogen element, boron element, silicon element, and the like.
  • the non-metallic element is fluorine
  • a fluorine-doped diamond-like carbon film is prepared, and the fluorine-doped diamond-like carbon film is used as the film to be deposited adjacent to the porous polyolefin membrane.
  • a modified separator is obtained on the surface of the negative electrode material, and the separator can improve its thermal stability, corrosion resistance, wettability of the separator and electrolyte, and reduce the dielectric constant, which is more beneficial to improve battery performance.
  • the non-metallic element is nitrogen
  • a nitrogen-doped diamond-like carbon film is prepared, and the nitrogen-doped diamond-like carbon film is used as the film to be deposited on the porous polyolefin membrane.
  • a modified separator is obtained on the surface adjacent to the negative electrode material, and the separator can improve its thermal stability, reduce resistivity, and more beneficially improve battery performance.
  • the film has a single-layer structure or a multi-layer structure.
  • the film has a single-layer structure, and the single-layer structure is a diamond-like carbon film; further preferably, the diamond-like film is selected from the group consisting of a non-hydrogen tetrahedral carbon film, a hydrogen-containing tetrahedral carbon film, and a non-hydrogen carbon At least one of a film, a hydrogen-containing carbon film, a polymer-like carbon film, and a graphitic carbon film.
  • the film has a single-layer structure, and the single-layer structure is a diamond-like carbon film doped with a single element.
  • the element is selected from any of metal elements such as lithium element, titanium element, aluminum element, tin element, zinc element, copper element, and non-metal elements such as fluorine element, nitrogen element, hydrogen element, boron element, silicon element, etc. One kind.
  • doped diamond-like film as a film deposited on the surface of the porous polyolefin separator adjacent to the negative electrode material can further improve the ion conductivity, thermal conductivity, toughness, and electrolyte wettability of the battery, which is beneficial to improve the film and
  • the bonding performance of the separator can further improve the stability and reduce the resistivity, and improve the cycle performance and rate performance of the battery.
  • the film has a multilayer structure. Adding a multi-layered film can improve the bonding performance of the layer structure in contact with the diaphragm and reduce the changes in the physical properties of the interface, thereby improving the contact between the diaphragm and the film material, improving the bonding ability, and making the film material have a strong bonding ability, not easy to fall off and Not easy to crack.
  • the film has a multilayer structure of two or more layers, and at least one layer in the multilayer structure is a diamond-like carbon film.
  • the film has a multi-layer structure of two or more layers, and the multi-layer structure is a diamond-like carbon film of the same material.
  • the film has a multi-layer structure of two or more layers, and the multi-layer structure is a diamond-like carbon film of different materials.
  • the film has a multilayer structure of two or more layers, and at least one layer in the multilayer structure is a single element diamond-like carbon film.
  • the film has a multilayer structure of two or more layers, and at least two layers in the multilayer structure are diamond-like films doped with elements, and different layer structures have different types of doped elements.
  • the thickness of the film is 1 to 3 ⁇ m. If the thickness is too thin, it cannot play the role of enhancing the strength of the diaphragm, and can not well hinder the growth of metal dendrites, change the growth direction of dendrites, and make them grow laterally, so as to prevent metal dendrites from piercing the diaphragm, and cannot improve The stability of the battery. If the thickness is too thick, the internal stress of the prepared film will be large, and it will be easily damaged during use, cracking and falling off, affecting long-term use.
  • the material of the porous polyolefin membrane is selected from at least one of polypropylene, polyethylene, three-layer polypropylene, polyethylene, and polypropylene.
  • the polyolefin-based diaphragm is a polyolefin-based material with sufficient porosity and an insulating effect
  • the structure of the polyolefin-based diaphragm is a membrane material with a macroscopic flat and a microscopic porous structure.
  • the thickness of the porous polyolefin membrane is 16-25 ⁇ m.
  • the porous polyolefin membrane is selected from polypropylene.
  • the porous polyolefin membrane is a porous polyolefin membrane with a single-layer structure or a multi-layer structure; further preferably, the porous polyolefin membrane has a multi-layer structure, wherein the different layer structures of the multi-layer structure are selected Porous polyolefins of different materials.
  • the porous polyolefin membrane has a multi-layer structure, wherein the different layer structures of the multi-layer structure select porous polyolefins of different materials.
  • the multi-layer structure is a first porous polypropylene layer, and polypropylene and polyethylene layers are arranged on either side of the first porous polypropylene layer, and the polypropylene and polyethylene layers are away from the first porous polypropylene layer.
  • One side of the porous polypropylene layer is provided with a second porous polypropylene layer to form a "sandwich structure".
  • the porous polyolefin membrane has a multi-layer structure, wherein the multi-layer structure is a first porous polypropylene layer, and a polyolefin is provided on any side of the first porous polypropylene layer. Acrylic or polyethylene layer.
  • the porous polyolefin membrane is a single-layer polypropylene with a thickness of 25 ⁇ m.
  • the modified separator for a metal negative electrode battery provided by the present invention includes a porous polyolefin separator and a thin film deposited at least on the surface of the porous polyolefin separator adjacent to the negative electrode material, wherein the thin film includes a diamond-like carbon film .
  • the porous polyolefin diaphragm is modified with a thin film
  • the thin film includes a diamond-like carbon film, which has strong chemical inertness, improves the oxidation resistance and corrosion resistance of the diaphragm; has strong adhesion and can be uniform It is deposited on the surface of the metal foil material to keep the modification effect even and smooth; the diamond-like carbon film has high strength, enhances the strength of the diaphragm, can hinder the growth of metal dendrites, change the growth direction of dendrites, and make them grow laterally. It prevents metal dendrites from piercing the diaphragm, effectively avoids short-circuit failure of the battery due to damage to the diaphragm, and improves the safety of battery use. At the same time, it can guide the uniform deposition of the negative electrode metal, stabilize the stability of the metal negative electrode, and further enhance the cycle stability of the battery.
  • the above-mentioned modified separator of the metal negative electrode battery is prepared by the following preparation method of the modified separator of the metal negative electrode battery.
  • the embodiment of the present invention also provides a method for preparing a modified separator of a metal negative electrode battery, the modified separator includes a porous polyolefin separator and a film deposited at least on the surface of the porous polyolefin separator adjacent to the negative electrode material , wherein the method for preparing the thin film is selected from any one of magnetron sputtering, plasma chemical vapor deposition, ion beam assisted deposition, pulsed laser deposition, or filtered cathode vacuum arc deposition.
  • a magnetron sputtering method is used to provide a thin film on the porous polyolefin membrane.
  • the method for preparing the modified separator of the metal negative electrode battery includes the following steps:
  • a porous polyolefin membrane is provided, and the porous polyolefin membrane is pre-treated; preferably, the pre-treatment step is: according to the size of the equipment, the porous polyolefin membrane
  • the diaphragm is cut into a porous polyolefin diaphragm material of suitable size and shape.
  • the porous polyolefin membrane is cut into a rectangle with a size of 15 cm ⁇ 3 cm.
  • the porous polyolefin membrane obtained by the pretreatment is placed in a vacuum coating equipment, a carbon target is installed, the equipment is evacuated and argon gas is introduced, the diaphragm is set to rotate, and the base is biased.
  • the furnace cavity is cleaned under the conditions of 50 ⁇ 55V pressure and 20 ⁇ 25W ion power.
  • the porous polyolefin membrane obtained by the pretreatment is placed on a circular base with a diameter of 20 cm.
  • the diaphragm is set to rotate, and the rotation speed of the diaphragm is 1 r/min.
  • the rotation speed is to achieve a large-area uniform deposition at one time. If it is not rotated, the deposition range is limited to directly below the target, and the rotation is too fast. There will be a danger of the substrate being separated, and contact with the inner wall of the wall will short-circuit and damage the equipment.
  • the vacuum in the equipment is 6-8 ⁇ 10 -3 Pa; the flow of the argon is 30 sccm.
  • the pressure is directly proportional to the ventilation. The greater the ventilation, the higher the pressure.
  • the pressure is usually controlled by controlling the flow of the same period.
  • argon is a very important protective gas for the plasma to be generated by the equipment initiation. If the gas flow is too small, it is difficult to initiate the ignition. If the gas flow is too large, it is wasteful and causes plasma instability.
  • the furnace chamber is cleaned under the conditions of a susceptor bias voltage of 50 ⁇ 55V and an ion body power of 20 ⁇ 25W.
  • the bias voltage is applied to change the plasma moving speed after ignition. The higher the bias voltage, the faster the moving speed. Therefore, a film with higher hardness and density can be obtained; the power of the power supply is also the main influencing factor of the structure and performance of the film.
  • the high power will generate more plasma and the temperature will rise in a short time, and the annealing effect will also be produced, and the film stress will be more If the power is too high, it will cause damage to the deposition target, while the power is too low to start.
  • the cleaning time of the oven cavity is 600 s. If the cleaning time is too long, it is of little significance to the preparation, but will increase the cost; if the cleaning time is too short, the cleaning will not be clean, and impurities will be introduced into the prepared film. .
  • step S03 after the cleaning of the furnace cavity is completed, a deposition process is performed under the condition of a power of 20-25W to obtain the modified diaphragm of the battery.
  • the time of the deposition treatment is 5 hours, wherein too large deposition power and too long deposition time will cause the thickness of the prepared film to be too thick, and the result will have an adverse effect on the battery; on the contrary, the deposition power is too small and The deposition time is too short to show the best effect of modification.
  • the modified diaphragm with the battery is cut into a desired size, and placed in a vacuum oven at 60° C. for 12 h for use.
  • the diamond-like carbon film is prepared by the following preparation method, and the preparation method includes the following steps:
  • G01 Provide a base material to pre-process the base material, wherein at least one side of the base material is a clean side;
  • the base material is selected from any one of quartz glass, stainless steel, PMMA, ceramic materials, polymers, and alloy foil materials.
  • a silicon wafer is selected as the base material.
  • the pre-processing method includes: putting the base material into an organic solvent volume for ultrasonic treatment, and drying the ultrasonic-treated base material.
  • the drying step is: drying the matrix material after the ultrasonic treatment with an electric hair dryer, and finally put the sample into an 80 °C blast drying oven for drying; the purpose of drying with an electric hair dryer It is to avoid traces of droplets on the surface of the base material.
  • the matrix material is sequentially put into acetone and absolute ethanol solution for ultrasonic cleaning 15 min, repeat three times; the purpose is to remove oil and impurities.
  • the added amount of the two solvents is approximately at least 30 mL, but the silicon wafer must be immersed.
  • step G02 the pre-processed matrix material is fixed in a plasma chemical vapor deposition chamber, evacuated to a pressure of 6-8 ⁇ 10-3 Pa, and argon at a flow rate of 30 sccm is applied, and a susceptor is applied.
  • the substrate material was cleaned under the condition of a bias voltage of 50V and a power of 20W.
  • argon is a very important protective gas for the plasma to be generated by the equipment initiation. If the gas flow is too small, it is difficult to initiate the ignition. If the gas flow is too large, it is wasteful and causes plasma instability.
  • the bias voltage is applied to change the plasma moving speed after ignition.
  • the cleaning time for cleaning the base material is 10-15 min.
  • the susceptor bias is set to 50 V
  • the carbon target deposition power is 20 W
  • the deposition time is controlled and different types of gases are mixed to prepare different hardness and different types of DLC films .
  • the deposition time is 15 min-10 h. Control the deposition time to prepare DLC films of different hardness and types.
  • the bias voltage of the susceptor is set to 50 V. If the bias voltage is too little, the DLC film is an ordinary amorphous DLC film or an amorphous carbon film with low hydrogen content; if the bias voltage is too much, it is a hydrogen-containing DLC film.
  • the invention provides a method for preparing a modified diaphragm of a metal negative battery.
  • the modified diaphragm of the battery has a simple preparation method, convenient operation, high safety, low cost, no damage to the diaphragm material itself, and can ensure the preparation
  • the modified diaphragm of the obtained battery is flat and uniform, which is conducive to subsequent reactions.
  • the present invention also provides a secondary battery.
  • the structure of the secondary battery is shown in FIG. 2.
  • the secondary battery includes a positive electrode current collector 1, a positive electrode active material 2, a solution 3, a separator 4, and The metal negative electrode 5, wherein the separator 4 includes a porous polyolefin separator 6 and a thin film 7 deposited on any side of the porous polyolefin separator 6.
  • the diaphragm is the above-mentioned modified diaphragm of a metal negative electrode battery or a modified diaphragm prepared by the above-mentioned method for preparing a modified diaphragm of a metal negative battery.
  • the positive electrode current collector is an alloy material or a composite material; further preferably, the material of the positive electrode current collector is selected from aluminum, magnesium, vanadium, copper, iron, tin, zinc, nickel, titanium, manganese, and aluminum. Any kind.
  • the cathode current collector is an alloy material containing at least one of the foregoing metal elements; in other embodiments, the cathode current collector is a composite material containing at least one of the foregoing metal elements.
  • the material of the positive electrode current collector is carbon-coated aluminum foil.
  • the positive electrode active material includes an active material, a conductive agent and a binder. Further preferably, the active material is selected from any material selected from lithium cobalt oxide, lithium iron phosphate, and nickel cobalt manganese ternary materials. In a preferred embodiment of the present invention, the positive electrode active material is lithium iron phosphate.
  • the conductive agent is selected from at least one of conductive carbon black, conductive carbon balls, conductive graphite, carbon nanotubes, conductive carbon fibers, graphene, and reduced graphene oxide.
  • the conductive agent is conductive carbon black.
  • the binder is selected from at least one of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, SBR rubber, and polyolefins.
  • the binder is polyvinylidene fluoride.
  • the mass percentage of the positive electrode material is 100%, the mass percentage of the positive electrode active material is 60-95%, the mass percentage of the conductive agent is 5-30%, and the mass percentage of the binder is The content is 5-10%.
  • the method for preparing the positive electrode includes the following steps:
  • the surface of the positive electrode current collector material is processed, and the processing method is a cleaning process, alternately cleaning with an organic solvent and deionized water to remove excess impurities.
  • the solvent is selected from N-methylpyrrolidone.
  • the temperature of the drying treatment is 80-85° C., and the time of the drying treatment is 11-12 hours.
  • the diaphragm is the above-mentioned modified diaphragm of a metal negative electrode battery or a modified diaphragm prepared by the above-mentioned method for preparing a modified diaphragm of a metal negative battery.
  • the modified diaphragm includes a porous polyolefin diaphragm and a film deposited on either side of the porous polyolefin diaphragm, wherein the film includes a diamond-like film material.
  • the porous polyolefin membrane is selected from single-layer polypropylene with a thickness of 25 ⁇ m; the diamond-like film material is a single-layer non-hydrogen tetrahedral (ta-C) film with a thickness of 1 ⁇ m .
  • the modified diaphragm is in the shape of a disc with a diameter of 16 mm.
  • the electrolyte is a certain amount of lithium salt electrolyte added to the non-aqueous solvent, and the resulting product is dissolved after thorough stirring.
  • the electrolyte has a concentration of 0.1-10 mol/L.
  • the lithium salt electrolyte is selected from lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium trifluoromethanesulfonate, lithium bisfluorosulfonimide, and bistrifluorosulfonamide.
  • the lithium salt electrolyte is selected from lithium hexafluorophosphate.
  • the non-aqueous solvent includes a mixture of one or more of esters, ethers, and sulfones, such as diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, Any one of dimethyl sulfone, dimethyl ether, 1,3-dioxolane, and ethylene carbonate.
  • the non-aqueous solvent is a mixture of ethylene carbonate and diethyl carbonate in a volume ratio of 1:1.
  • the method for preparing the electrolyte is as follows: weigh a certain amount of two or more lithium salt electrolytes and add them to the non-aqueous solvent, stir and dissolve them sufficiently to obtain the desired electrolyte.
  • the metal negative electrode is selected from any one of lithium, sodium, potassium, and zinc.
  • the present invention also provides a secondary battery, which includes a positive electrode current collector, a positive electrode, a separator, an electrolyte, and a metal negative electrode; wherein, the separator is the modified separator of the above-mentioned metal negative battery or is composed of the above-mentioned metal negative electrode.
  • the modified diaphragm prepared by the method for preparing the modified diaphragm of the battery. Using the above-mentioned modified diaphragm as the diaphragm of the metal negative electrode battery can effectively hinder the growth of metal dendrites, prevent the metal dendrites from piercing the diaphragm, improve the safety of the metal metal negative battery, and improve the cycle stability and high performance of the energy storage device. Better performance under magnification.
  • the present invention also provides a method for preparing a secondary battery, which includes the following steps:
  • Preparation of the positive electrode Weigh the positive electrode active material, conductive agent and binder in a certain proportion, add a suitable solvent and mix thoroughly to form a uniform slurry to make the positive electrode active material layer; provide the positive electrode current collector, clean it, and then remove the positive electrode active material The layer is uniformly coated on the surface of the positive electrode current collector with a certain thickness, and after the positive electrode active material layer is completely dried, it is cut into a certain size to prepare a positive electrode.
  • D05 Perform battery assembly. Provide an inert gas or an anhydrous and oxygen-free environment, stack or roll the positive electrode, the separator, and the negative electrode into a battery core in sequence, drop an appropriate amount of electrolyte to completely infiltrate the separator, and package it in the casing , You can get the secondary battery.
  • the preparation method of the above secondary battery is simple and fast.
  • the modified diaphragm prepared by the method for preparing the modified diaphragm of the metal negative electrode battery is used as the battery diaphragm, so that the secondary battery has excellent electrochemical performance, good cycle stability and long service life.
  • the positive electrode, the negative electrode, the electrolyte, and the separator of the battery are respectively prepared and assembled, wherein the separator is a modified separator of a fluorine metal negative battery.
  • the modified diaphragm of the metal negative battery is prepared by a magnetron sputtering method, and the preparation method includes the following steps:
  • a porous polyolefin membrane is provided, and the porous polyolefin membrane is pre-treated; the porous polyolefin membrane is a porous polypropylene membrane;
  • the flow rate is 30 sccm.
  • the diaphragm is set to rotate at a speed of 1 r/min, and the oven cavity is cleaned under the conditions of a base bias of 50V and an ion body power of 20W, and the cleaning time is 10 min;
  • the deposition process is performed under the condition of 20W power.
  • the deposition process time is 5 hours.
  • the modified diaphragm with the battery is cut into 16 mm and placed in a vacuum oven. After 12 h at 60°C, the modified separator of the battery can be obtained.
  • the modified diaphragm is used as the diaphragm; the lithium foil is used as the negative electrode; in the electrolyte, the lithium salt electrolyte is selected from lithium hexafluorophosphate, and the non-aqueous solvent is a mixture of ethylene carbonate and diethyl carbonate with a volume ratio of 1:1.
  • the concentration is 1 mol/L LiPF 6 ;
  • the positive electrode is prepared with lithium iron phosphate as the positive electrode active material, and then the battery is assembled.
  • the separator is a modified separator of a fluorine metal negative battery.
  • the porous polyolefin diaphragm is a porous polypropylene diaphragm
  • the porous The polyolefin separator is a porous polyethylene separator
  • the porous polyolefin diaphragm is a porous polypropylene diaphragm
  • the porous The polyolefin separator is a porous polyethylene separator
  • the porous polyolefin diaphragm is a porous polypropylene diaphragm
  • the porous The polyolefin separator is a porous polyethylene separator; the "deposition treatment time is 5 h” is replaced by the "deposition treatment time is 2 h”; the other steps are the same as in Example 1, and the battery is manufactured.
  • the positive electrode, the negative electrode, the electrolyte, and the separator of the battery are respectively prepared and assembled, wherein the separator is a modified separator of a fluorine metal negative battery.
  • the modified diaphragm of the metal negative battery is prepared by a filtered cathode vacuum arc deposition method, and the preparation method includes the following steps:
  • the vacuum value is 5x10 -5 Pa (about 3h); after vacuuming, open the argon valve and let in argon (Ar) gas with a flow rate of 20 SCCM; turn on the pulse bias power supply after the gas flow stabilizes, and set
  • the constant pulse bias power supply is 100-500V, which is applied to the sample stage; the beam bias power supply is turned on, so that Ar will start to bombard the substrate and clean up for 10-30 minutes; the high-voltage arc power supply is turned on, the power is 100-1500W, and the deposition time is controlled as In 5 hours, the modified separator of the battery can be obtained.
  • the modified diaphragm is used as the diaphragm; the lithium foil is used as the negative electrode; in the electrolyte, the lithium salt electrolyte is selected from lithium hexafluorophosphate, and the non-aqueous solvent is a mixture of ethylene carbonate and diethyl carbonate with a volume ratio of 1:1.
  • the concentration is 1 mol/L LiPF 6 ;
  • the positive electrode is prepared with lithium iron phosphate as the positive electrode active material, and then the battery is assembled.
  • the separator is a modified separator of a fluorine metal negative battery.
  • the positive electrode, the negative electrode, the electrolyte, and the separator of the battery are respectively prepared and assembled, wherein the separator is a modified separator of a fluorine metal negative battery.
  • the modified diaphragm of the metal negative electrode battery is prepared by a plasma-enhanced chemical vapor deposition method, and the preparation method includes the following steps:
  • the modified diaphragm is used as the diaphragm; the lithium foil is used as the negative electrode; in the electrolyte, the lithium salt electrolyte is selected from lithium hexafluorophosphate, and the non-aqueous solvent is a mixture of ethylene carbonate and diethyl carbonate with a volume ratio of 1:1.
  • the concentration is 1 mol/L LiPF 6 ;
  • the positive electrode is prepared with lithium iron phosphate as the positive electrode active material, and then the battery is assembled.
  • the separator is a modified separator of a fluorine metal negative battery.
  • base bias voltage 50V is replaced with “base bias voltage 52V”; other steps As in Example 1, a battery was manufactured.
  • base bias voltage 50V is replaced with “base bias voltage 54V”; other steps As in Example 1, a battery was manufactured.
  • base bias voltage 50V is replaced with “base bias voltage 55V”; other steps As in Example 1, a battery was manufactured.
  • Example 1 Compared with the method of Example 1, "Sodium foil as the negative electrode” is replaced with “Sodium foil as the negative electrode”; the other steps are the same as in Example 1, and the battery is manufactured.
  • the lithium salt electrolyte is selected from lithium hexafluorophosphate
  • the lithium salt electrolyte is selected from lithium tetrafluoroborate
  • the lithium salt electrolyte is selected from lithium hexafluorophosphate
  • the lithium salt electrolyte is selected from lithium perchlorate
  • the non-aqueous solvent is a mixture of ethylene carbonate and diethyl carbonate with a volume ratio of 1:1
  • the non-aqueous solvent is dimethyl carbonate
  • the non-aqueous solvent is a mixture of ethylene carbonate and diethyl carbonate with a volume ratio of 1:1
  • the non-aqueous solvent is ethyl methyl carbonate
  • Example 2 Compared with the embodiment of Example 1, "was prepared to give a concentration of 1 mol / L LiPF 6" replace “prepared at a concentration of 0.1 mol / L LiPF 6"; and other steps the same as in Example 1, the battery manufacture.
  • Example 1 The batteries prepared by the preparation methods of the foregoing Examples 1 to 18 and Comparative Examples 1 to 2 were cycled at a rate of 10C and the specific performance of each battery was analyzed. The analysis results are shown in Table 1, which can be obtained from Table 1.
  • the modified separator is It is prepared by using the magnetron sputtering method of Example 1 and depositing on the PP film for 5 hours.
  • the capacity retention rate is ⁇ 75%, and the maximum capacity retention rate is 83%.
  • the modified diaphragm adopts the magnetron sputtering method of Example 7 and is deposited on the PE film for 10 hours Prepared.
  • the secondary battery adopting the modified diaphragm of the metal anode battery can effectively increase the number of cycles and the capacity retention rate, so that the secondary battery has better electrochemical performance, and the cycle stability of the secondary battery is improved.
  • Example 1 195 80% Example 2 110 79% Example 3 194 80% Example 4 182 81% Example 5 130 80% Example 6 100 80% Example 7 105 83% Example 8 102 80% Example 9 191 82% Example 10 190 80% Example 11 185 77% Example 12 120 80% Example 13 165 76% Example 14 130 80% Example 15 90 75% Example 16 126 80% Example 17 120 81% Example 18 115 80% Comparative example 1 97 79% Comparative example 2 176 80%
  • Example 1 Select the secondary battery prepared in Example 1 with the modified separator as the separator, lithium iron phosphate as the positive electrode active material, and 1 mol/L LiPF 6 as the electrolyte.
  • the method of controlled sputtering was prepared by deposition treatment on the PP film for 5 hours; the secondary battery prepared in Example 6 was selected, wherein, in the preparation method of the secondary battery, the "deposition treatment time is 0 h", Other conditions are the same as the preparation method of Example 1.
  • the performance of the secondary battery of Example 1 and Example 6 is analyzed and compared, and the performance analysis is shown in Figure 3. The cycle number of each battery is analyzed and implemented.
  • the cycle life of the secondary battery prepared in Example 1 reached 200 cycles; while the cycle life of the secondary battery prepared in Example 6 was about 100 cycles; the specific capacity of each battery was analyzed, and the secondary battery prepared in Example 1, When the number of cycles reaches 200 cycles, the specific discharge capacity still remains 60 mAh/g; the coulombic efficiency is close to 100%; and the secondary battery prepared in Example 6 has the specific discharge capacity reduced to 100 cycles when the cycle reaches 100 cycles. 60 mAh/g. It can be seen that the secondary battery prepared in Example 1 uses the modified separator as the separator, lithium iron phosphate as the positive electrode active material, and 1 mol/L LiPF 6 as the electrolyte.
  • Example 1 The method of magnetron sputtering was prepared by deposition treatment on a PP film for 5 hours; the secondary battery can maintain a better number of cycles and a higher specific capacity.

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Abstract

本申请提供了一种金属负极电池的改性隔膜，所述改性隔膜包括多孔聚烯烃隔膜及至少沉积在所述多孔聚烯烃隔膜邻近负极材料的表面的薄膜，其中，所述薄膜包括类金刚石薄膜。类金刚石薄膜具有较高的强度，增强了隔膜的强度，能够阻碍金属枝晶的生长，改变枝晶的生长方向，使其横向生长，避免金属枝晶刺穿隔膜，有效避免电池因隔膜受损而短路失效，提高了电池使用的安全性，同时能够引导负极金属均匀沉积，提高金属负极的稳定性，进而大幅增强电池的循环稳定性。

Description

一种金属负极电池的改性隔膜、制备方法及应用 技术领域
本发明涉及储能器件技术领域，尤其涉及一种金属负极电池的改性隔膜、制备方法及应用。
 背景技术
当前，传统的锂金属电池（LIBs）能量密度和功率密度有限，已经无法满足人们日益增长的对更高能量密度电池的迫切需求。开发更高能量密度、更安全环保的储能电池是目前的研究热点。
以锂金属电池为例，其具有能量密度高、低密度、低氧化还原电位等优点，在消费电子产品、电动交通工具、电网调峰、储能电源、航空航天等领域有巨大应用前景。锂金属电池包括正极集流体、正极、隔膜、电解液和负极；锂金属电池能大大改善电池性能，增强电池的电量持久力，大幅改观电力存储的经济效益，促进消费类电子产品的升级转型，对人类生活具有重大意义，其中，所使用的隔膜选自织造膜、非织造膜（无纺布）、微孔膜、复合膜、隔膜纸、碾压膜、聚烯烃隔膜等几种，但是，在使用过程中存在以下问题，（1）锂金属负极在不断的沉积-剥离的过程中容易生成枝晶，枝晶会刺穿隔膜，导致电池短路而失效；（2）金属锂与电解液在界面发生反应形成的固体电解质层（SEI膜）随时间而不断增厚，界面阻抗不断增加，库伦效率降低，电池容量衰减；（3）由于锂金属负极体积在充放电过程中不断变化，SEI膜不稳定，在沉积-剥离过程中，不断的生成-破裂-再生成，消耗金属锂和电解液。上述问题不仅影响了电池使用的安全性能和使用寿命，还影响了电池在高倍率下的性能，限制了锂金属电池的使用，因此，迫切需要一种方法以防止隔膜刺穿或减弱锂枝晶生长对锂金属电池的影响，提高锂金属电池安全性和稳定性。
 技术问题
本发明的目的在于提供一种金属负极电池的改性隔膜、制备方法及应用，旨在解决现有技术中电池隔膜易被金属枝晶刺穿而影响电池的安全性和稳定性的问题。
 技术解决方案
为实现上述发明目的，本发明采用的技术方案如下：
一种金属负极电池的改性隔膜，所述改性隔膜包括多孔聚烯烃隔膜及至少沉积在所述多孔聚烯烃隔膜邻近负极材料的表面的薄膜，其中，所述薄膜包括类金刚石薄膜。
以及，一种金属负极电池的改性隔膜的制备方法，所述改性隔膜包括多孔聚烯烃隔膜及至少沉积在所述多孔聚烯烃隔膜邻近负极材料的表面的薄膜，其中，所述薄膜的制备方法选自磁控溅射法、等离子化学气相沉积法、离子束辅助沉积法、脉冲激光沉积法或过滤阴极真空电弧沉积法的任意一种。
以及，一种二次电池，所述二次电池包括正极集流体、正极活性材料、隔膜、电解液和金属负极；其中，所述隔膜为上述的金属负极电池的改性隔膜或由上述金属负极电池的改性隔膜的制备方法制备得到的改性隔膜。
本发明所提供的金属负极电池的改性隔膜，所述改性隔膜包括多孔聚烯烃隔膜及至少沉积在所述多孔聚烯烃隔膜邻近负极材料的表面的薄膜，其中，所述薄膜包括类金刚石薄膜。采用薄膜对所述多孔聚烯烃隔膜进行修饰，且所述薄膜包括类金刚石薄膜，具有以下优点：
类金刚石薄膜具有较强的化学惰性，提高了隔膜抗氧化性和耐腐蚀性；类金刚石薄膜具有较强的附着力，能够均匀化沉积在隔膜的表面，保持修饰效果均匀平整；类金刚石薄膜具有较高的强度，增强了隔膜的强度，能够阻碍金属枝晶的生长，改变枝晶的生长方向，使其横向生长，避免金属枝晶刺穿隔膜，有效避免电池因隔膜受损而短路失效，提高了电池使用的安全性，同时能够引导负极金属均匀沉积，提高金属负极的稳定性，进而大幅增强电池的循环稳定性。
本发明还提供一种金属负极电池的改性隔膜的制备方法，所述改性隔膜包括多孔聚烯烃隔膜及至少沉积在所述多孔聚烯烃隔膜邻近负极材料的表面的薄膜，其中，所述薄膜的制备方法选自磁控溅射法、等离子化学气相沉积法、离子束辅助沉积法、脉冲激光沉积法或过滤阴极真空电弧沉积法的任意一种。所述电池的改性隔膜制备方法简单、操作方便，安全性高，成本较低，不会对隔膜材料本身造成破坏，同时能保证制备得到的电池的改性隔膜平整均匀，有利于后续反应。
 有益效果
本发明还提供一种二次电池，所述二次电池包括正极集流体、正极、隔膜、电解液和金属负极；其中，所述隔膜为上述的金属负极电池的改性隔膜或由上述金属负极电池的改性隔膜的制备方法制备得到的改性隔膜。采用上述改性隔膜作为金属负极电池的隔膜，能够有效地阻碍金属枝晶的生长，避免金属枝晶刺穿隔膜，改善金属负极电池的安全性同时，提高储能器件的循环稳定性以及高倍率下有较好的性能。
 附图说明
图1是本发明实施例提供的金属负极电池的改性隔膜结构。
图2是本发明实施例提供的二次电池的结构示意图。
图3是本发明实施例1中方法制备得到的二次电池和实施例6中方法制备得到的二次电池的电池性能分析图。
 本发明的实施方式
为使本发明实施例的目的、技术方案和技术效果更加清楚，下面将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发明一部分实施例，而不是全部的实施例。结合本发明中的实施例，本领域普通技术人员在没有作出创造性劳动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。
在本发明的描述中，需要理解的是，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。在本发明的描述中，“多个”的含义是两个或两个以上，除非另有明确具体的限定。
本发明实例提供一种金属负极电池的改性隔膜，所述金属负极电池的改性隔膜的结构如图1所示，所述改性隔膜包括多孔聚烯烃隔膜1及至少沉积在所述多孔聚烯烃隔膜1邻近负极材料的表面的薄膜2。
在本发明另一实施中，所述改性隔膜包括多孔聚烯烃隔膜及至少沉积在所述多孔聚烯烃隔膜两个表面的薄膜。
具体的，所述薄膜包括类金刚石薄膜。采用薄膜对所述多孔聚烯烃隔膜进行修饰，所述薄膜包括类金刚石薄膜，类金刚石薄膜具有较强的化学惰性，提高了隔膜抗氧化性和耐腐蚀性；具有较强的附着力，能够均匀化沉积在隔膜的表面，保持修饰效果均匀平整；类金刚石薄膜具有较高的强度，增强了隔膜的强度，能够阻碍金属枝晶的生长，改变枝晶的生长方向，使其横向生长，避免金属枝晶刺穿隔膜，有效避免电池因隔膜受损而短路失效，提高了电池使用的安全性，同时能够引导负极金属均匀沉积，稳定金属负极的稳定性，进一步增强电池的循环稳定性。
具体的，类金刚石具有高硬度、高电阻率、良好光学性能，同时又具有较强的化学惰性的非晶碳材料。类金刚石主要包含sp 2和sp 3两种杂化键，而在含氢的类金刚石薄膜中还存在一定数量的C-H键。优选的，所述类金刚石薄膜选自非晶碳膜、四面体非晶碳膜、类聚合物非晶态碳膜、类金刚石碳膜、类石墨碳膜的至少一种。在本发明优选实施例中，所述元素掺杂类金刚石薄膜中类金刚石薄膜选自非晶碳膜或四面体非晶碳膜，其中，非晶碳膜主要是由sp 3和sp 2键碳原子相互混杂的三维网络构成，四面体非晶碳膜主要是由超过80%的sp 3键碳原子为骨架构成。在本发明优选实施例中，所述类金刚石薄膜为非氢四面体（ta-C）薄膜。
优选的，所述薄膜选自由类金刚石材料形成的薄膜、掺杂元素的类金刚石薄膜的至少一种。在本发明优选实施例中，所述薄膜为掺杂元素的类金刚石薄膜，采用掺杂元素的类金刚石薄膜作为薄膜材料，能够进一步提高电池的导电性、导离子率、韧性，有利于改善薄膜与隔膜的结合性能，能够进一步提高稳定性及降低电阻率，提高电池的循环性能以及倍率性能。其中，所述掺杂元素为金属元素或非金属元素。
优选的，采用掺杂元素的类金刚石薄膜作为沉积在多孔聚烯烃隔膜的薄膜，当所述掺杂元素为金属元素时，能够进一步提高电池的导离子率、韧性，有利于改善薄膜与隔膜的结合性能，提高电池的循环性能以及倍率性能。进一步优选的，所述掺杂元素选自铝元素、钛元素、锡元素、锌元素、铜元素等任意一种。在本发明一实施例中，当所述金属元素为铝元素，制备得到铝元素掺杂的类金刚石薄膜，以所述铝元素掺杂的类金刚石薄膜作为薄膜沉积在多孔聚烯烃隔膜的邻近负极材料的表面得到改性隔膜，提高电池的导离子率和导热率，锂沉积过程还可以与铝形成铝锂合金从而减少锂枝晶生成，提高电池的循环性能以及倍率性能。在本发明另一实施例中，当所述金属元素为钛元素，制备得到钛元素掺杂的类金刚石薄膜，以所述钛元素掺杂的类金刚石薄膜作为薄膜沉积在多孔聚烯烃隔膜的邻近负极材料的表面得到改性隔膜，提高了所述改性隔膜的韧性，改善了薄膜与隔膜的结合性能，显著增强了其附着力。
优选的，采用掺杂元素的类金刚石薄膜作为沉积在多孔聚烯烃隔膜的薄膜，当所述掺杂元素为非金属元素，能进一步提高稳定性及降低电阻率，提高电池的循环性能以及倍率性能。优选的，所述非金属元素选自氟元素、氮元素、氢元素、硼元素、硅元素等的任意一种。在本发明一实施例中，当所述非金属元素为氟元素，制备得到氟元素掺杂的类金刚石薄膜，以所述氟元素掺杂的类金刚石薄膜作为薄膜沉积在多孔聚烯烃隔膜的邻近负极材料的表面得到改性隔膜，所述隔膜能够提高其热稳定性、耐腐蚀性、隔膜与电解液浸润性以及降低介电常数，更有利提高电池性能。在本发明另一实施例中，当所述非金属元素为氮元素，制备得到氮元素掺杂的类金刚石薄膜，以所述氮元素掺杂的类金刚石薄膜作为薄膜沉积在多孔聚烯烃隔膜的邻近负极材料的表面得到改性隔膜，所述隔膜能够提高其热稳定性、降低电阻率，更有利提高电池性能。
优选的，所述薄膜为单层结构或多层结构。优选的，所述薄膜为单层结构，且所述单层结构为类金刚石薄膜；进一步优选的，所述类金刚石薄膜选自非氢四面体碳膜、含氢四面体碳膜、非氢碳膜、含氢碳膜、类高聚物碳膜和类石墨碳膜的至少一种。
优选的，所述薄膜为单层结构，且所述单层结构为单一元素掺杂的类金刚石薄膜。进一步优选的，所述元素选自锂元素、钛元素、铝元素、锡元素、锌元素、铜元素等金属元素和氟元素、氮元素、氢元素、硼元素、硅元素等非金属元素的任意一种。采用掺杂元素的类金刚石薄膜作为薄膜沉积在所述多孔聚烯烃隔膜邻近负极材料的表面，能够进一步提高电池的导离子率、导热性能、韧性、与电解液浸润性等，有利于改善薄膜与隔膜的结合性能，能够进一步提高稳定性及降低电阻率，提高电池的循环性能以及倍率性能。
优选的，所述薄膜为多层结构。添加多层结构的薄膜，能够改善与隔膜接触的层结构的结合性能，减少界面物理性能的变化，从而改善隔膜与薄膜材料的接触，提高结合能力，使薄膜材料结合能力强，不容易脱落且不易开裂。
优选的，所述薄膜为两层或两层以上的多层结构，且多层结构中的至少一层为类金刚石薄膜。在本发明一实施例中，所述薄膜为两层或两层以上的多层结构，且多层结构中为相同材料的类金刚石薄膜。在本发明另一实施例中，所述薄膜为两层或两层以上的多层结构，且多层结构中为不同材料的类金刚石薄膜。
优选的，所述薄膜为两层或两层以上的多层结构，且多层结构中的至少一层为单一元素的类金刚石薄膜。优选的，所述薄膜为两层或两层以上的多层结构，且多层结构中的至少两层为掺杂元素的类金刚石薄膜，且不同的层结构中掺杂元素的类型不同。
优选的，所述薄膜的厚度为1~3 μm。若厚度太薄，则无法起到所述增强隔膜强度的作用，无法较好地阻碍金属枝晶的生长，改变枝晶的生长方向，使其横向生长，避免金属枝晶刺穿隔膜，无法提高电池的稳定性。若厚度太厚，则制备得到的薄膜内应力较大，使用中易损坏，易开裂和脱落，影响长期使用。
优选的，所述多孔聚烯烃隔膜的材料选自聚丙烯、聚乙烯、三层聚丙烯、聚乙烯、聚丙烯的至少一种。具体的，所述聚烯烃类隔膜为具有足够孔隙率和具有绝缘作用的聚烯烃类材料，所述聚烯烃类隔膜的结构为宏观上平整、微观上多孔结构的膜材。优选的，所述多孔聚烯烃隔膜的厚度为16~25 μm。在本发明优选实施例中，所述多孔聚烯烃隔膜选自聚丙烯。
优选的，所述多孔聚烯烃隔膜为单层结构或多层结构的多孔聚烯烃隔膜；进一步优选的，所述多孔聚烯烃隔膜为多层结构，其中，所述多层结构的不同层结构选用不同材料的多孔聚烯烃。在本发明一实施例中，所述多孔聚烯烃隔膜为多层结构，其中，所述多层结构的不同层结构选用不同材料的多孔聚烯烃。其中，所述多层结构为第一多孔聚丙烯层，在所述第一多孔聚丙烯层任意一面设置聚丙烯与聚乙烯层，在所述聚丙烯与聚乙烯层背离所述第一多孔聚丙烯层的一面设置第二多孔聚丙烯层，形成“三明治结构”。在本发明另一实施例中，所述多孔聚烯烃隔膜为多层结构，其中，所述多层结构为第一多孔聚丙烯层，在所述第一多孔聚丙烯层任意一面设置聚丙烯或聚乙烯层。在本发明优选实施例中，所述多孔聚烯烃隔膜为单层聚丙烯，厚度为25 μm。
本发明所提供的金属负极电池的改性隔膜，所述改性隔膜包括多孔聚烯烃隔膜及至少沉积在所述多孔聚烯烃隔膜邻近负极材料的表面的薄膜，其中，所述薄膜包括类金刚石薄膜。采用薄膜对所述多孔聚烯烃隔膜进行修饰，所述薄膜包括类金刚石薄膜，类金刚石薄膜具有较强的化学惰性，提高了隔膜抗氧化性和耐腐蚀性；具有较强的附着力，能够均匀化沉积在金属箔材料的表面，保持修饰效果均匀平整；类金刚石薄膜具有较高的强度，增强了隔膜的强度，能够阻碍金属枝晶的生长，改变枝晶的生长方向，使其横向生长，避免金属枝晶刺穿隔膜，有效避免电池因隔膜受损而短路失效，提高了电池使用的安全性，同时能够引导负极金属均匀沉积，稳定金属负极的稳定性，进一步增强电池的循环稳定性。
上述金属负极电池的改性隔膜由以下金属负极电池的改性隔膜的制备方法制备得到。
相应的，本发明实施例还提供了一种金属负极电池的改性隔膜的制备方法，所述改性隔膜包括多孔聚烯烃隔膜及至少沉积在所述多孔聚烯烃隔膜邻近负极材料的表面的薄膜，其中，所述薄膜的制备方法选自磁控溅射法、等离子化学气相沉积法、离子束辅助沉积法、脉冲激光沉积法或过滤阴极真空电弧沉积法的任意一种。在本发明优选实施例中，采用磁控溅射法在多孔聚烯烃隔膜上设置薄膜。
优选的，所述金属负极电池的改性隔膜的制备方法包括如下步骤：
S01. 提供一多孔聚烯烃隔膜，将所述多孔聚烯烃隔膜进行前处理；
S02. 将前处理得到的多孔聚烯烃隔膜放置于真空镀膜设备内，安装碳靶，将设备内抽真空并通入氩气，设置所述隔膜转动，在基座偏压50~55V，离子体的功率20 ~25W的条件下进行炉腔清洗；
S03. 待炉腔清洗结束后，在功率20 ~25W的条件下进行沉积处理，即可得到所述电池的改性隔膜。
具体的，在上述步骤S01中，提供一多孔聚烯烃隔膜，将所述多孔聚烯烃隔膜进行前处理；优选的，所述前处理的步骤为：依据设备的大小，将所述多孔聚烯烃隔膜裁剪成大小合适、形状合适的多孔聚烯烃隔膜材料。在本发明优选实施例中，将所属多孔聚烯烃隔膜裁剪成矩形，大小为15 cm×3 cm。
具体的，在上述步骤S02中，将前处理得到的多孔聚烯烃隔膜放置于真空镀膜设备内，安装碳靶，将设备内抽真空并通入氩气，设置所述隔膜转动，在基座偏压50~55V，离子体的功率20 ~25W的条件下进行炉腔清洗。优选的，所述将前处理得到的多孔聚烯烃隔膜放置于真空镀膜设备内的步骤中，所述前处理得到的多孔聚烯烃隔膜放置于直径为20 cm的圆形基座。进一步优选的，设置所述隔膜转动，所述隔膜转动的转速为1 r/min，转速是为了实现一次性大面积均匀沉积，若不旋转，沉积范围仅限靶材正下方，而旋转过快则会产生基材脱离危险，与墙体内壁接触则会短路毁伤设备。
优选的，将设备内抽真空并通入氩气的步骤中，设备内的真空为6～8×10 -3 Pa；通入氩气的气流量为30 sccm。压强和通气量成正比，通气量越大，压强越高，通常通过控制同期流量来控制压强。其中，氩气是设备启辉产生等离子体的很重要保护气体，气流量过小很难启辉，气流量过大浪费，且导致等离子体不稳定。
优选的，在基座偏压50~55V，离子体的功率20~25W的条件下进行炉腔清洗，施加偏压是为了改变启辉后等离子体移动速度，偏压越大，移动速度越快，从而可以得到硬度和密度更高的薄膜；电源功率同样是薄膜结构与性能的主要影响因素，功率高短时间产生更多等离子体且温度会升高，也会产生退火效果，薄膜应力会更大，功率过高会导致沉积靶材损坏，而功率过低无法启辉。优选的，所述炉腔清洗的时间为600 s，若清洗时间过长，对制备无太多意义，反而增加成本；若清洗时间过短，会因清洗不干净，会给制备的薄膜引入杂质。
在步骤S03中，待炉腔清洗结束后，在功率20 ~25W的条件下进行沉积处理，即可得到所述电池的改性隔膜。优选的，所述沉积处理的时间为5 h，其中，沉积功率过大和沉积时间过长都会导致制备的薄膜的厚度过厚，其结果都给电池带来不利影响；反之，沉积功率过小和沉积时间过短，都不能展现修饰的最佳效果。
优选的，沉积处理结束后，将有所述电池的改性隔膜裁切成所需尺寸，置于真空烘箱中，60℃下12 h，备用。
在一些实施例，所述类金刚石薄膜由如下制备方法制备得到，所述制备方法包括如下步骤：
G01. 提供一基体材料，将所述基体材料进行前处理，其中，所述基体材料至少有一面为光净的一面；
G02. 将前处理得到的基体材料固定在等离子化学气相沉积室中，抽真空至压强为6～8×10 -3 Pa，通入流量为30 sccm氩气，施加基座偏压50V，在功率为20W的条件下清洗所述基体材料；
G03. 通入氩气，设置基座偏压为50 V，碳靶沉积的功率为20 W，控制沉积时间和掺入不同类型气体，制备不同硬度、不同种类的DLC薄膜。
具体的，在上述步骤G01中，优选的，所述基体材料选自石英玻璃、不锈钢、PMMA、陶瓷材料和高分子、合金箔材等的任意一种。在本发明优选实施例中，选择硅片作为基体材料。
优选的，将所述基体材料进行前处理的步骤中，所述前处理的方法包括：将所述基体材料放入有机溶剂容进行超声处理后，烘干超声处理后的基体材料。进一步优选的，所述烘干的步骤为：将超声处理后的基体材料用电热吹风机将基体吹干，最后再将样品放入80 ℃鼓风干燥箱中烘干；采用电热吹风机吹干的目的是为了避免基体材料表面有液滴痕迹。在本发明优选实施例中，将所述基体材料依次放入丙酮、无水乙醇溶液中超声清洗15 min，重复三次；目的都是为了将油污和杂质除尽。优选的，所述两种溶剂的添加量大概至少30 mL，但必须浸没硅片。
具体的，在步骤G02中，将前处理得到的基体材料固定在等离子化学气相沉积室中，抽真空至压强为6～8×10-3 Pa，通入流量为30 sccm氩气，施加基座偏压50V，在功率为20W的条件下清洗所述基体材料。其中，氩气是设备启辉产生等离子体的很重要保护气体，气流量过小很难启辉，气流量过大浪费，且导致等离子体不稳定。施加偏压是为了改变启辉后等离子体移动速度，偏压越大，移动速度越快，从而可以得到硬度和密度更高的薄膜；电源功率同样是薄膜结构与性能的主要影响因素，功率高短时间产生更多等离子体且温度会升高，也会产生退火效果，薄膜应力会更大，功率过高会导致沉积靶材损坏，而功率过低无法启辉。
优选的，清洗所述基体材料的清洗时间为10~15 min。
具体的，在上述步骤G03中通入氩气，设置基座偏压为50 V，碳靶沉积的功率为20 W，控制沉积时间和掺入不同类型气体，制备不同硬度、不同种类的DLC薄膜。优选的，所述沉积时间为15 min~10 h。控制沉积时间，以制备不同硬度、不同种类的DLC薄膜。具体的，设置基座偏压为50 V,若施加偏压过少，DLC薄膜为普通无定型DLC薄膜或少氢含量无定型碳膜；若施加偏压过多，则为含氢DLC薄膜。
本发明提供的金属负极电池的改性隔膜的制备方法，所述电池的改性隔膜制备方法简单、操作方便，安全性高，成本较低，不会对隔膜材料本身造成破坏，同时能保证制备得到的电池的改性隔膜平整均匀，有利于后续反应。
相应的，本发明还提供一种二次电池，所述二次电池的结构如图2所示，所述二次电池包括正极集流体1、正极活性材料2、解液3、隔膜4、和金属负极5，其中，所述隔膜4包括多孔聚烯烃隔膜6及沉积在所述多孔聚烯烃隔膜6任意一面的薄膜7。
其中，所述隔膜为上述的金属负极电池的改性隔膜或由上述的金属负极电池的改性隔膜的制备方法制备得到的改性隔膜。
优选的，所述正极集流体为合金材料或复合材料；进一步优选的，所述正极集流体的材料选自铝、镁、钒、铜、铁、锡、锌、镍、钛、锰、铝的任意一种。在一些实施例中，所述正极集流体为含有至少一种上述金属元素的合金材料；在另一些实施例中，所述正极集流体为含有至少一种上述金属元素的复合材料。在本发明优选实施例中，所述正极集流体的材料为涂碳铝箔。
优选的，所述正极活性材料包括活性材料、导电剂和粘结剂。进一步优选的，所述活性材料选自钴酸锂、磷酸铁锂、镍钴锰三元材料的任意一种材料。在本发明优选实施例中，所述正极活性材料为磷酸铁锂。
优选的，所述导电剂选自导电炭黑、导电碳球、导电石墨、碳纳米管、导电碳纤维、石墨烯、还原氧化石墨烯中的至少一种。在本发明优选实施例中，所述导电剂为导电炭黑。
优选的，所述粘结剂选自聚偏氟乙烯、聚四氟乙烯、聚乙烯醇、羧甲基纤维素、SBR橡胶、聚烯烃类中的至少一种。在本发明优选实施例中，所述粘结剂为聚偏氟乙烯。
优选的，以所述正极材料的质量为100%，所述正极活性材料的质量百分含量为60-95%，导电剂的质量百分含量为5-30%，粘结剂的质量百分含量为5-10%。
在本发明优选实施例中，所述正极的制备方法包括如下步骤：
Q01. 提供一正极集流体材料，对所述正极集流体材料的表面进行处理；
Q02. 按照上述添加量称取正极活性材料、导电剂以及粘结剂，加入溶剂进行充分混合形成均匀浆料；将所述浆料均匀涂覆于正极集流体任意一面，形成正极活性材料层，干燥处理，待完全干燥后压制并裁切，得到所需尺寸的电池正极。
具体的，上述步骤Q01中，对所述正极集流体材料的表面进行处理，所述处理的方法为清洗处理，用有机溶剂和去离子水交替清洗，除去多余的杂质。
具体的，在上述步骤Q02中，所述溶剂选自N-甲基吡咯烷酮。优选的，所述干燥处理的步骤中，干燥处理的温度为80~85 ℃，干燥处理的时间为11~12小时。
具体的，所述隔膜为上述的金属负极电池的改性隔膜或由上述的金属负极电池的改性隔膜的制备方法制备得到的改性隔膜。所述改性隔膜包括多孔聚烯烃隔膜及沉积在所述多孔聚烯烃隔膜任意一面的薄膜，其中，所述薄膜包括类金刚石薄膜材料。在本发明优选实施例中，所述多孔聚烯烃隔膜选自单层聚丙烯，厚度为25 μm；所述类金刚石薄膜材料为单层非氢四面体（ta-C）薄膜，厚度为1 μm。所述改性隔膜为圆片形状，直径为16 mm。
优选的，所述电解液是一定量的锂盐电解质加入到非水溶剂中，充分搅拌后溶解所得产物，优选的，所述电解液的且浓度为0.1-10 mol/L。
进一步优选的，所述电解液中，所述锂盐电解质选自六氟磷酸锂、四氟硼酸锂、高氯酸锂、三氟甲磺酸锂、双氟磺酰亚胺锂、双三氟磺酰亚胺锂氯化锂、氟化锂、硫酸锂、碳酸锂、磷酸锂、硝酸锂、二氟草酸硼酸锂、六氟砷酸锂、双草酸硼酸锂的任意一种。在本发明优选实施例中，所述锂盐电解质选自六氟磷酸锂。
进一步优选的，所述电解液中，所述非水溶剂包括酯类、醚类、砜类中的一种或多种的混合，例如碳酸二乙酯、碳酸二甲酯、碳酸甲乙酯、二甲基砜或二甲醚、1,3-二氧戊环、碳酸乙烯酯的任意一种。在本发明优选实施例中，所述非水溶剂为体积比1:1的碳酸乙烯酯、碳酸二乙酯的混合物。
在本发明优选实施例中，所述电解液的配制方法如下：称取一定量的两种或两种以上的锂盐电解质加入到非水溶剂中，充分搅拌溶解，得到所需电解液。
优选的，所述金属负极选自锂、钠、钾、锌的任意一种。
本发明还提供一种二次电池，所述二次电池包括正极集流体、正极、隔膜、电解液和金属负极；其中，所述隔膜为上述的金属负极电池的改性隔膜或由上述金属负极电池的改性隔膜的制备方法制备得到的改性隔膜。采用上述改性隔膜作为金属负极电池的隔膜，能够有效地阻碍金属枝晶的生长，避免金属枝晶刺穿隔膜，改善金属金属负极电池的安全性同时，提高储能器件的循环稳定性以及高倍率下有较好的性能。
相应的，本发明还提供一种二次电池的制备方法，所述制备方法包括如下步骤：
D01. 制备负极：将锂金属箔片进行裁切，直接作为电池负极；
D02. 配制电解液：称取一定量的锂盐电解质加入到非水溶剂中，充分搅拌，得浓度为0.1-10 mol/L的电解液；
D03. 制备隔膜：选用上述金属负极电池的改性隔膜的制备方法制备得到的改性隔膜；
D04. 制备正极：按一定比例称取正极活性材料、导电剂以及粘结剂，加入适当溶剂充分混合成均匀浆料制成正极活性材料层；提供正极集流体，清洗干净，然后将正极活性材料层以一定厚度均匀涂覆于正极集流体表面，待所述正极活性材料层完全干燥后裁切成一定尺寸制备得到正极。
D05. 进行电池组装。提供惰性气体或无水无氧环境，将所述正极、所述隔膜、所述负极依次堆叠或卷绕成电池芯，滴加适量电解液使所述隔膜完全浸润，并封装于所述外壳内，即可得到所述二次电池。
上述二次电池的制备方法简单，快捷。采用上述金属负极电池的改性隔膜的制备方法制备得到的改性隔膜作为电池隔膜，使得该二次电池电化学性能较为优异，具有良好的循环稳定性和较长的使用寿命。
现以具体实施例进一步进行说明。
实施例1
分别制备电池正极、负极、电解液、隔膜并进行组装，其中所述隔膜为氟金属负极电池的改性隔膜。
制备金属负极电池的改性隔膜：所述金属负极电池的改性隔膜采用磁控溅射的方法进行制备，所述制备方法包括如下步骤：
提供一多孔聚烯烃隔膜，将所属多孔聚烯烃隔膜进行前处理；所述多孔聚烯烃隔膜为多孔聚丙烯隔膜；
将前处理得到的多孔聚烯烃隔膜放置于真空镀膜设备内，安装碳靶，将设备内抽真空并通入氩气，控制设备内的真空为6×10 -3 Pa；通入氩气的气流量为30 sccm。设置所述隔膜转动，转速为1 r/min，在基座偏压50V，离子体的功率20W的条件下进行炉腔清洗，清洗时间为10 min；
待炉腔清洗结束后，在功率20W的条件下进行沉积处理，沉积处理时间为5 h，沉积处理结束后，将有所述电池的改性隔膜裁切成16 mm，置于真空烘箱中，60℃下12 h，即可得到所述电池的改性隔膜。
以所述改性隔膜为隔膜；锂箔作为负极；电解液中，所述锂盐电解质选自六氟磷酸锂，非水溶剂为体积比1:1的碳酸乙烯酯、碳酸二乙酯的混合物，制备得到浓度为1 mol/L LiPF 6；以磷酸铁锂为正极活性材料制备正极，再进行组合装配电池。上述制备得到的电池中，隔膜为氟金属负极电池的改性隔膜。
实施例2
与实施例1的方式相比，所述金属负极电池的改性隔膜采用磁控溅射的方法进行制备的步骤中，“沉积处理时间为5 h”替换成“沉积处理时间为10 h”；其他步骤和实施例1中相同，制造电池。
实施例3
与实施例1的方式相比，所述金属负极电池的改性隔膜采用磁控溅射的方法进行制备的步骤中，“沉积处理时间为5 h”替换成“沉积处理时间为2 h”；其他步骤和实施例1中相同，制造电池。
实施例4
与实施例1的方式相比，所述金属负极电池的改性隔膜采用磁控溅射的方法进行制备的步骤中，“沉积处理时间为5 h”替换成“沉积处理时间为1 h”；其他步骤和实施例1中相同，制造电池。
实施例5
与实施例1的方式相比，所述金属负极电池的改性隔膜采用磁控溅射的方法进行制备的步骤中，“沉积处理时间为5 h”替换成“沉积处理时间为0.5 h”；其他步骤和实施例1中相同，制造电池。
实施例6
与实施例1的方式相比，所述金属负极电池的改性隔膜采用磁控溅射的方法进行制备的步骤中，“所述多孔聚烯烃隔膜为多孔聚丙烯隔膜”替换成“所述多孔聚烯烃隔膜为多孔聚乙烯隔膜”；其他步骤和实施例1中相同，制造电池。
实施例7
与实施例1的方式相比，所述金属负极电池的改性隔膜采用磁控溅射的方法进行制备的步骤中，“所述多孔聚烯烃隔膜为多孔聚丙烯隔膜”替换成“所述多孔聚烯烃隔膜为多孔聚乙烯隔膜”；“沉积处理时间为5 h”替换成“沉积处理时间为10 h”；其他步骤和实施例1中相同，制造电池。
实施例8
与实施例1的方式相比，所述金属负极电池的改性隔膜采用磁控溅射的方法进行制备的步骤中，“所述多孔聚烯烃隔膜为多孔聚丙烯隔膜”替换成“所述多孔聚烯烃隔膜为多孔聚乙烯隔膜”；“沉积处理时间为5 h”替换成“沉积处理时间为2 h”；其他步骤和实施例1中相同，制造电池。
实施例9
分别制备电池正极、负极、电解液、隔膜并进行组装，其中所述隔膜为氟金属负极电池的改性隔膜。
制备金属负极电池的改性隔膜：所述金属负极电池的改性隔膜采用过滤阴极真空电弧沉积法的方法进行制备，所述制备方法包括如下步骤：
选定高纯度、圆柱状碳靶材作为靶材；并提供一多孔聚丙烯薄膜作为基材，并固定至设备上；
关闭设备真空室，抽真空值5x10 -5 Pa （约3h）；抽真空后，打开氩气阀门通入，流量为20 SCCM的氩（Ar）气；待气流稳定后打开脉冲偏压电源，设定脉冲偏压电源为100-500V，施加在样品台上；开启射偏电源，使得Ar启辉，轰击基材，清理10-30 min；开启高压电弧电源，功率100-1500W，控制沉积时间为5 h，即可得到所述电池的改性隔膜。
以所述改性隔膜为隔膜；锂箔作为负极；电解液中，所述锂盐电解质选自六氟磷酸锂，非水溶剂为体积比1:1的碳酸乙烯酯、碳酸二乙酯的混合物，制备得到浓度为1 mol/L LiPF 6；以磷酸铁锂为正极活性材料制备正极，再进行组合装配电池。上述制备得到的电池中，隔膜为氟金属负极电池的改性隔膜。
实施例10
与实施例9的方式相比，所述金属负极电池的改性隔膜采用过滤阴极真空电弧沉积的方法进行制备的步骤中，“沉积处时间为5 h”替换成“沉积时间为10 h”；其他步骤和实施例9中相同，制造电池。
实施例11
与实施例9的方式相比，所述金属负极电池的改性隔膜采用过滤阴极真空电弧沉积的方法进行制备的步骤中，“沉积处时间为5 h”替换成“沉积时间为12h”；其他步骤和实施例9中相同，制造电池。
实施例12
与实施例9的方式相比，所述金属负极电池的改性隔膜采用过滤阴极真空电弧沉积的方法进行制备的步骤中，“沉积处时间为5 h”替换成“沉积时间为1 h”；其他步骤和实施例9中相同，制造电池。
实施例13
与实施例9的方式相比，所述金属负极电池的改性隔膜采用过滤阴极真空电弧沉积的方法进行制备的步骤中，“沉积处时间为5 h”替换成“沉积时间为0.5 h”；其他步骤和实施例9中相同，制造电池。
实施例14
分别制备电池正极、负极、电解液、隔膜并进行组装，其中所述隔膜为氟金属负极电池的改性隔膜。
制备金属负极电池的改性隔膜：所述金属负极电池的改性隔膜采用等离子体增强化学的气相沉积的方法进行制备，所述制备方法包括如下步骤：
选取聚丙烯薄膜作为基材，并固定在设备内部；关闭设备真空室，抽真空值5x10 -5 Pa （约3h）；打开氩气阀门通入，流量为20 SCCM的氩（Ar）气；待气流稳定后打开脉冲偏压电源，设定脉冲偏压电源为100-500V，施加在样品台上；开启射偏电源，使得Ar启辉，轰击基材，清理10-30 min；打开碳源（甲烷，乙炔，四氟甲烷，三甲基硼烷等）气体阀门，控制流量为5-30 SCCM，同时打开Ar气体，流量20 SCCM，带气流稳定；开启射频电源，功率控制在10-100 W，产生碳源氩气混合等离子，设置沉积时间为5h，即可得到所述电池的改性隔膜。
以所述改性隔膜为隔膜；锂箔作为负极；电解液中，所述锂盐电解质选自六氟磷酸锂，非水溶剂为体积比1:1的碳酸乙烯酯、碳酸二乙酯的混合物，制备得到浓度为1 mol/L LiPF 6；以磷酸铁锂为正极活性材料制备正极，再进行组合装配电池。上述制备得到的电池中，隔膜为氟金属负极电池的改性隔膜。
实施例15
与实施例14的方式相比，所述金属负极电池的改性隔膜采用等离子体增强化学的气相沉积的方法进行制备的步骤中，“沉积处时间为5 h”替换成“沉积时间为10 h”；其他步骤和实施例9中相同，制造电池。
实施例16
与实施例14的方式相比，所述金属负极电池的改性隔膜采用等离子体增强化学的气相沉积的方法进行制备的步骤中，“沉积处时间为5 h”替换成“沉积时间为2 h”；其他步骤和实施例9中相同，制造电池。
实施例17
与实施例14的方式相比，所述金属负极电池的改性隔膜采用等离子体增强化学的气相沉积的方法进行制备的步骤中，“沉积处时间为5 h”替换成“沉积时间为1 h”；其他步骤和实施例9中相同，制造电池。
实施例18
与实施例14的方式相比，所述金属负极电池的改性隔膜采用等离子体增强化学的气相沉积的方法进行制备的步骤中，“沉积处时间为5 h”替换成“沉积时间为0.5 h”；其他步骤和实施例9中相同，制造电池。
对比例1
与实施例1的方式相比，所述金属负极电池的改性隔膜采用磁控溅射的方法进行制备的步骤中，“沉积处理时间为5 h”替换成“沉积处理时间为0 h”；其他步骤和实施例1中相同，制造电池。
对比例2
与实施例9的方式相比，所述金属负极电池的改性隔膜采用过滤阴极真空电弧沉积的方法进行制备的步骤中，“沉积处时间为5 h”替换成“沉积时间为0 h”；其他步骤和实施例9中相同，制造电池。
实施例19
与实施例1的方式相比，所述金属负极电池的改性隔膜采用磁控溅射的方法进行制备的步骤中，“控制设备内的真空为6×10 -3 Pa”替换成“控制设备内的真空为7×10 -3 Pa”；其他步骤和实施例1中相同，制造电池。
实施例20
与实施例1的方式相比，所述金属负极电池的改性隔膜采用磁控溅射的方法进行制备的步骤中，“控制设备内的真空为6×10 -3 Pa”替换成“控制设备内的真空为8×10 -3 Pa”；其他步骤和实施例1中相同，制造电池。
实施例21
与实施例1的方式相比，所述金属负极电池的改性隔膜采用磁控溅射的方法进行制备的步骤中，“基座偏压50V”替换成“基座偏压52V”；其他步骤和实施例1中相同，制造电池。
实施例22
与实施例1的方式相比，所述金属负极电池的改性隔膜采用磁控溅射的方法进行制备的步骤中，“基座偏压50V”替换成“基座偏压54V”；其他步骤和实施例1中相同，制造电池。
实施例23
与实施例1的方式相比，所述金属负极电池的改性隔膜采用磁控溅射的方法进行制备的步骤中，“基座偏压50V”替换成“基座偏压55V”；其他步骤和实施例1中相同，制造电池。
实施例24
与实施例1的方式相比，所述金属负极电池的改性隔膜采用磁控溅射的方法进行制备的步骤中，“离子体的功率20 W”替换成“离子体的功率22 W”；其他步骤和实施例1中相同，制造电池。
实施例25
与实施例1的方式相比，所述金属负极电池的改性隔膜采用磁控溅射的方法进行制备的步骤中，“离子体的功率20 W”替换成“离子体的功率25 W”；其他步骤和实施例1中相同，制造电池。
实施例26
与实施例1的方式相比，所述金属负极电池的改性隔膜采用磁控溅射的方法进行制备的步骤中，“离子体的功率20 W”替换成“离子体的功率25 W”；其他步骤和实施例1中相同，制造电池。
实施例27
与实施例1的方式相比，所述金属负极电池的改性隔膜采用磁控溅射的方法进行制备的步骤中，“在功率20W的条件下进行沉积处理”替换成“在功率22W的条件下进行沉积处理”；其他步骤和实施例1中相同，制造电池。
实施例28
与实施例1的方式相比，所述金属负极电池的改性隔膜采用磁控溅射的方法进行制备的步骤中，“在功率20W的条件下进行沉积处理”替换成“在功率25W的条件下进行沉积处理”；其他步骤和实施例1中相同，制造电池。
实施例29
与实施例1的方式相比，“钠箔作为负极”替换成“钠箔作为负极”；其他步骤和实施例1中相同，制造电池。
实施例30
与实施例1的方式相比，“钾箔作为负极”替换成“钾箔作为负极”；其他步骤和实施例1中相同，制造电池。
实施例31
与实施例1的方式相比，“锌箔作为负极”替换成“锌箔作为负极”；其他步骤和实施例1中相同，制造电池。
实施例32
与实施例1的方式相比，“所述锂盐电解质选自六氟磷酸锂”替换成“所述锂盐电解质选自四氟硼酸锂”；其他步骤和实施例1中相同，制造电池。
实施例33
与实施例1的方式相比，“所述锂盐电解质选自六氟磷酸锂”替换成“所述锂盐电解质选自高氯酸锂”；其他步骤和实施例1中相同，制造电池。
实施例34
与实施例1的方式相比，“非水溶剂为体积比1:1的碳酸乙烯酯、碳酸二乙酯的混合物”替换成“非水溶剂为碳酸二甲酯”；其他步骤和实施例1中相同，制造电池。
实施例35
与实施例1的方式相比，“非水溶剂为体积比1:1的碳酸乙烯酯、碳酸二乙酯的混合物”替换成“非水溶剂为碳酸甲乙酯”；其他步骤和实施例1中相同，制造电池。
实施例36
与实施例1的方式相比，“制备得到浓度为1 mol/L LiPF 6”替换成“制备得到浓度为0.1 mol/L LiPF 6”；其他步骤和实施例1中相同，制造电池。
实施例37
与实施例1的方式相比，“以磷酸铁锂为正极活性材料制备正极”替换成“以钴酸锂为正极活性材料制备正极”；其他步骤和实施例1中相同，制造电池。
实施例38
与实施例1的方式相比，“以磷酸铁锂为正极活性材料制备正极”替换成“以镍钴锰三元材料为正极活性材料制备正极”；其他步骤和实施例1中相同，制造电池。
将上述实施例1~18、对比例1~2的制备方法制备得到的电池，在10C倍率下循环并分析各个电池的具体性能，分析结果如表1，由表1可得，实施例1~18制备得到的隔膜为制备得到的金属负极电池的改性隔膜的二次电池中，循环次数≥90次，循环次数最高为195次，循环次数最高的二次电池中，所述改性隔膜为采用实施例1磁控溅射的方法，在PP膜上沉积处理5小时制备得到的。容量保持率≥75%，容量保持率最高为83%，容量保持率最高的二次电池中，所述改性隔膜为采用实施例7磁控溅射的方法，在PE膜上沉积处理10小时制备得到的。采用金属负极电池的改性隔膜的二次电池，可以有效地提高循环次数和容量保持率，使该二次电池具有较优异的电化学性能，提高了该二次电池的循环稳定性。
表1
  循环次数 容量保持率
实施例1 195 80%
实施例2 110 79%
实施例3 194 80%
实施例4 182 81%
实施例5 130 80%
实施例6 100 80%
实施例7 105 83%
实施例8 102 80%
实施例9 191 82%
实施例10 190 80%
实施例11 185 77%
实施例12 120 80%
实施例13 165 76%
实施例14 130 80%
实施例15 90 75%
实施例16 126 80%
实施例17 120 81%
实施例18 115 80%
对比例1 97 79%
对比例2 176 80%
选取实施例1制备得到的以改性隔膜作为隔膜，磷酸铁锂为正极活性材料，以1 mol/L LiPF 6为电解液的二次电池，其中，所述改性隔膜为采用实施例1磁控溅射的方法，在PP膜上沉积处理5小时制备得到的；选取实施例6制备得到的二次电池，其中，所述二次电池的制备方法中，“沉积处理时间为0 h”，其他条件与实施例1的制备方法均相同；对上述实施例1和实施例6的二次电池的性能进行分析比较，性能分析如图3所示，对各电池的循环圈数进行分析，实施例1制备得到的二次电池循环寿命达到200圈；而实施例6制备得到的二次电池循环寿命为100圈左右；对各电池的比容量进行分析，实施例1制备得到的二次电池，在循环圈数达到200圈时，放电比容量仍保持60 mAh/g；库伦效率接近100%；而实施例6制备得到的二次电池，在循环全书达到100圈时，放电比容量已降低至60 mAh/g。由此可见，实施例1制备得到的以改性隔膜作为隔膜，磷酸铁锂为正极活性材料，以1 mol/L LiPF 6为电解液的二次电池，其中，所述改性隔膜为采用实施例1磁控溅射的方法，在PP膜上沉积处理5小时制备得到的；所述二次电池能够保持更好的循环圈数以及更高的比容量。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种金属负极电池的改性隔膜，其特征在于，所述改性隔膜包括多孔聚烯烃隔膜及至少沉积在所述多孔聚烯烃隔膜邻近负极材料的表面的薄膜，其中，所述薄膜包括类金刚石薄膜。
  2. 根据权利要求1所述的金属负极电池的改性隔膜，其特征在于，所述薄膜选自由类金刚石材料形成的薄膜、掺杂元素的类金刚石薄膜的至少一种。
  3. 根据权利要求2所述的金属负极电池的改性隔膜，其特征在于，所述类金刚石薄膜选自非氢四面体碳膜、含氢四面体碳膜、非氢碳膜、含氢碳膜、类高聚物碳膜和类石墨碳膜的至少一种。
  4. 根据权利要求1~3任一所述的金属负极电池的改性隔膜，其特征在于，所述薄膜为单层结构或多层结构，和/或；
    所述薄膜为单层结构，且所述单层结构为单一元素掺杂的类金刚石薄膜，和/或；
    所述薄膜为两层或两层以上的多层结构，且多层结构中的至少一层为类金刚石薄膜，和/或；
    所述薄膜为两层或两层以上的多层结构，且多层结构中的至少一层为单一元素的类金刚石薄膜，和/或；
    所述薄膜为两层或两层以上的多层结构，且多层结构中的至少两层为掺杂元素的类金刚石薄膜，且不同的层结构中掺杂元素的类型不同。
  5. 根据权利要求1~3任一所述的金属负极电池的改性隔膜，其特征在于，所述薄膜的厚度为1~3 μm。
  6. 根据权利要求1~3任一所述的金属负极电池的改性隔膜，其特征在于，所述多孔聚烯烃隔膜的材料选自聚丙烯、聚乙烯、三层聚丙烯、聚乙烯、聚丙烯的至少一种。
  7. 根据权利要求1~3任一所述的金属负极电池的改性隔膜，其特征在于，所述多孔聚烯烃隔膜为单层结构或多层结构的多孔聚烯烃隔膜；和/或，
    所述多孔聚烯烃隔膜为多层结构，其中，所述多层结构的不同层结构选用不同材料的多孔聚烯烃。
  8. 一种金属负极电池的改性隔膜的制备方法，其特征在于，所述改性隔膜包括多孔聚烯烃隔膜及至少沉积在所述多孔聚烯烃隔膜邻近负极材料的表面的薄膜，其中，所述薄膜的制备方法选自磁控溅射法、等离子化学气相沉积法、离子束辅助沉积法、脉冲激光沉积法或过滤阴极真空电弧沉积法的任意一种。
  9. 根据权利要求8所述的金属负极电池的改性隔膜的制备方法，其特征在于，所述薄膜的制备方法包括如下步骤：
    提供一多孔聚烯烃隔膜，将所述多孔聚烯烃隔膜进行前处理；
    经前处理得到的多孔聚烯烃隔膜放置于真空镀膜设备内，安装碳靶，将设备内抽真空并通入氩气，设置所述隔膜转动，在基底偏压50~55V，离子体的功率20 ~25W的条件下进行炉腔清洗；
    待炉腔清洗结束后，在功率20 ~25W的条件下进行沉积处理，即可得到所述电池的改性隔膜。
  10. 一种二次电池，其特征在于，所述二次电池包括正极集流体、正极活性材料、隔膜、电解液和金属负极；其中，所述隔膜为上述权利要求1~7任一所述的金属负极电池的改性隔膜或由上述权利要求8~9任一所述的金属负极电池的改性隔膜的制备方法制备得到的改性隔膜。
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