WO2023133805A1 - 一种用于锂离子二次电池的正极复合材料、正极和电池 - Google Patents

一种用于锂离子二次电池的正极复合材料、正极和电池 Download PDF

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WO2023133805A1
WO2023133805A1 PCT/CN2022/072029 CN2022072029W WO2023133805A1 WO 2023133805 A1 WO2023133805 A1 WO 2023133805A1 CN 2022072029 W CN2022072029 W CN 2022072029W WO 2023133805 A1 WO2023133805 A1 WO 2023133805A1
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positive electrode
secondary battery
alkali metal
ion secondary
negative electrode
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PCT/CN2022/072029
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English (en)
French (fr)
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李振华
吴夏逸
徐佳伟
杨子钰
傅寒立
徐硕言
李星
牛少军
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宁德时代新能源科技股份有限公司
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Priority to PCT/CN2022/072029 priority Critical patent/WO2023133805A1/zh
Priority to EP22899634.4A priority patent/EP4243125A4/en
Priority to CN202280031674.0A priority patent/CN117223131A/zh
Priority to US18/332,727 priority patent/US20230352680A1/en
Publication of WO2023133805A1 publication Critical patent/WO2023133805A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/04—Processes of manufacture in general
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    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present application relates to the field of batteries, in particular to a positive electrode composite material for a lithium ion secondary battery, a positive electrode of a lithium ion secondary battery using the positive electrode composite material, a lithium ion secondary battery and an electrical device.
  • lithium-ion secondary batteries have been widely used in energy storage power systems such as hydropower, thermal power, wind power and solar power stations, as well as power tools, electric bicycles, electric motorcycles, etc.
  • energy storage power systems such as hydropower, thermal power, wind power and solar power stations, as well as power tools, electric bicycles, electric motorcycles, etc.
  • Lithium-ion secondary batteries mainly rely on the movement of lithium ions between the positive and negative electrodes to work. During the charge and discharge process, lithium ions are intercalated and extracted back and forth between the two electrodes. During charging, lithium ions are extracted from the positive electrode, inserted into the negative electrode through the electrolyte, and the negative electrode is in a lithium-rich state. The opposite is true during discharge.
  • the negative electrode material (such as graphite) continues to expand/shrink with the intercalation/extraction of lithium ions during charge and discharge, resulting in a solid electrolyte interface film (sometimes below) Referred to as SEI film) is constantly damaged/repaired, resulting in continuous thickening of by-products and swelling.
  • SEI film solid electrolyte interface film
  • the continuous expansion/contraction of the negative electrode material with the intercalation/extraction of lithium ions will result in a decrease in the cohesive force between the particles, resulting in the rearrangement of the particles and the increase in the thickness of the negative electrode, resulting in a continuous increase in the expansion force of the lithium-ion secondary battery during use. Once this expansion force exceeds the expansion force threshold of the chemical system, it will lead to accelerated cell cycle attenuation, failure to meet quality assurance requirements or even thermal runaway. Therefore, the existing battery structure still needs to be improved.
  • the present application is made in view of the above-mentioned problems, and its purpose is to provide a method that can reduce or eliminate SEI film damage caused by negative electrode material deformation, reduce side reactions, reduce cell expansion force, thereby improving cell life and improving safety performance.
  • Positive electrode composite materials for lithium-ion secondary batteries are used.
  • the first aspect of the present application provides a positive electrode composite material for a lithium ion secondary battery, which comprises a positive electrode active material and an alkali metal oxide represented by the formula AmGOn , wherein A represents At least one element selected from Na and K and optional Li, G represents at least one element selected from Fe, Ni, Co, Mn, Ru, Ir, Sn, Cr, Nb, Mo, V and Ti , m is 1-6, and n is 1-4.
  • Na ions and/or K ions with larger ionic radii are used to open the negative electrode material, reducing or eliminating lithium ions with smaller ionic radii.
  • the expansion/contraction deformation of the negative electrode material caused by repeated embedding/extraction in the negative electrode material reduces or eliminates the damage of the SEI film caused by the deformation of the negative electrode material, reduces side reactions, and reduces the expansion force of the cell, thereby improving the life of the cell and improving safety performance .
  • the above - mentioned alkali metal oxide is at least A sort of.
  • Na ions and/or K ions can be more reliably used to expand the negative electrode material, thereby obtaining the above-mentioned technical effect.
  • the content of the alkali metal oxide is 0.1% to 10% by weight, preferably 0.5% to 4% by weight relative to the total of 100% by weight of the positive electrode active material and the alkali metal oxide.
  • the alkali metal oxide is higher than 0.1 wt%, a sufficient amount of Na and K ions can be intercalated in the negative electrode, the negative electrode material can be well stretched, and the improvement effect on circulation and expansion is excellent.
  • the alkali metal oxide is less than 10wt%, the initial expansion of the negative electrode will not be large due to the insertion of a large amount of Na and K plasma into the negative electrode, and there will not be much space inside the cell to absorb the expansion, so the energy density of the battery is high.
  • the second aspect of the present application also provides a positive electrode for a lithium ion secondary battery, which includes the positive electrode composite material for a lithium ion secondary battery according to the first aspect of the present application.
  • a lithium-ion secondary battery with high energy density, high cell life and high safety performance.
  • the third aspect of the present application also provides a positive electrode of a lithium ion secondary battery, which includes: a positive electrode current collector, a positive electrode active material layer containing a positive electrode active material, and an alkali metal oxide layer containing an alkali metal oxide, the above-mentioned Alkali metal oxides are represented by the formula AmGOn , wherein A represents at least one element selected from Na and K and optionally Li, and G represents an element selected from Fe , Ni, Co, Mn, Ru, Ir, Sn , Cr, Nb, Mo, V and Ti at least one element, m is 1-6, and n is 1-4.
  • Na ions and/or K ions with larger ionic radii can be used to open the negative electrode material, reducing or eliminating lithium ions due to the smaller ionic radius in the negative electrode material.
  • the expansion/contraction deformation of the negative electrode material caused by repeated embedding/extraction in the battery reduces or eliminates the SEI film damage caused by the deformation of the negative electrode material, reduces side reactions, and reduces the expansion force of the cell, thereby improving the life of the cell and improving safety performance.
  • the above - mentioned alkali metal oxide is at least A sort of.
  • Na ions and/or K ions can be more reliably used to expand the negative electrode material, thereby obtaining the above-mentioned technical effects.
  • the alkali metal oxide layer is located between the positive electrode current collector and the positive electrode active material layer, or on the positive electrode active material layer.
  • the content of the alkali metal oxide is 0.1% by weight relative to the total of 100% by weight of the positive electrode active material contained in the above-mentioned positive electrode active material layer and the alkali metal oxide contained in the above-mentioned alkali metal oxide layer. ⁇ 10% by weight, preferably 0.5% to 4% by weight.
  • the alkali metal oxide is higher than 0.1 wt%, a sufficient amount of Na and K ions can be intercalated in the negative electrode, the negative electrode material can be well stretched, and the improvement effect on circulation and expansion is excellent.
  • the alkali metal oxide is less than 10wt%, the initial expansion of the negative electrode will not increase due to the insertion of a large amount of Na and K plasma into the negative electrode, and there will not be much space inside the battery to absorb the expansion, so the energy density of the battery is high.
  • the fourth aspect of the present application also provides a lithium ion secondary battery, which includes the positive electrode according to the second aspect or the third aspect of the present application, and also includes a negative electrode.
  • the anode includes an anode active material
  • the anode active material includes at least one selected from carbon materials, metal or nonmetal compounds, coatings of the above compounds, and dopants of the above compounds.
  • the above-mentioned carbon material contains at least one selected from graphite, hard carbon and soft carbon
  • the above-mentioned metal or non-metallic compound contains oxides selected from silicon, selenium, sulfur, phosphorus, tin, titanium or vanadium.
  • the coating of the above compound includes: a coating obtained by coating the above metal or non-metal compound with graphite, soft carbon or hard carbon
  • the dopant of the above-mentioned compound includes: a dopant obtained by doping the above-mentioned metal or nonmetal compound with at least one element selected from Mg, Ni, Co, and Mn.
  • the metal or metalloid compound includes at least one selected from SiO 2 , SiO, SnO 2 , TiO 2 , SiS 2 and TiS 2 .
  • the fifth aspect of the present application also provides an electrical device, which includes the secondary battery of the fourth aspect of the present application. Since the electrical device includes the above-mentioned secondary battery, it has all the beneficial effects of the secondary battery.
  • FIG. 1 is a schematic diagram of a secondary battery according to an embodiment of the present application.
  • FIG. 2 is an exploded view of the secondary battery according to one embodiment of the present application shown in FIG. 1 .
  • FIG. 3 is a schematic diagram of a battery module according to an embodiment of the present application.
  • FIG. 4 is a schematic diagram of a battery pack according to an embodiment of the present application.
  • FIG. 5 is an exploded view of the battery pack according to one embodiment of the present application shown in FIG. 4 .
  • FIG. 6 is a schematic diagram of an electrical device in which a secondary battery is used as a power source according to an embodiment of the present application.
  • the positive electrode composite material for a lithium ion secondary battery of the present application the positive electrode of a lithium ion secondary battery using the positive electrode composite material, the lithium ion secondary battery, and the utility model are specifically disclosed in detail with reference to the drawings as appropriate.
  • Embodiment of an electrical device Embodiment of an electrical device.
  • unnecessary detailed descriptions may be omitted.
  • detailed descriptions of well-known items and repeated descriptions of substantially the same configurations may be omitted. This is to avoid the following description from becoming unnecessarily lengthy and to facilitate the understanding of those skilled in the art.
  • the drawings and the following descriptions are provided for those skilled in the art to fully understand the present application, and are not intended to limit the subject matter described in the claims.
  • ranges disclosed herein are defined in terms of lower and upper limits, and a given range is defined by selecting a lower limit and an upper limit that define the boundaries of the particular range. Ranges defined in this manner may be inclusive or exclusive and may be combined arbitrarily, ie any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, the following ranges are all expected: 1-3, 1-4, 1-5, 2- 3, 2 ⁇ 4 and 2 ⁇ 5.
  • the numerical range “a ⁇ b” represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers.
  • the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this article, and "0-5" is only an abbreviated representation of the combination of these values.
  • a certain parameter is an integer ⁇ 2
  • the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed in sequence, and may also include steps (b) and (a) performed in sequence.
  • steps (c) means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c) , may also include steps (a), (c) and (b), may also include steps (c), (a) and (b) and so on.
  • the “comprising” and “comprising” mentioned in this application mean open or closed.
  • the “comprising” and “comprises” may mean that other components not listed may also be included or included, or only listed components may be included or included.
  • the term "or” is inclusive unless otherwise stated.
  • the phrase "A or B” means “A, B, or both A and B.” More specifically, the condition "A or B” is satisfied by either of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists) ; or both A and B are true (or exist).
  • a positive electrode composite material for a lithium ion secondary battery which includes a positive electrode active material and an alkali metal oxide represented by the formula A m GO n , wherein A represents a group selected from Na and K At least one element in and optional Li, G represents at least one element selected from Fe, Ni, Co, Mn, Ru, Ir, Sn, Cr, Nb, Mo, V and Ti, m is 1 to 6, and n is 1-4.
  • the alkali metal oxide represented by the formula A m GO n may be used alone or in combination of two or more.
  • the inventors of the present application have found that during the use of lithium-ion secondary batteries, as lithium ions in the positive electrode active material are intercalated/extracted in the negative electrode material (such as graphite), the negative electrode material continues to expand/shrink, and the charge and discharge During the process, the SEI film is continuously damaged/repaired, resulting in the continuous thickening of by-products and causing swelling.
  • the continuous expansion/contraction of the negative electrode material with the intercalation/extraction of lithium ions will result in a decrease in the cohesive force between the particles, resulting in the rearrangement of the particles and the increase in the thickness of the negative electrode, resulting in a continuous increase in the expansion force of the lithium-ion secondary battery during use. This increase in expansion force will lead to accelerated cell cycle attenuation and poor safety performance.
  • the positive electrode composite material contains the alkali metal oxide shown in the above-mentioned AmGOn , and the Na ion and/or K ion with a larger ionic radius is used to open the negative electrode material, reducing or eliminating the negative electrode due to the smaller lithium ion radius.
  • the expansion/contraction deformation of the negative electrode material caused by repeated embedding/extraction in the material reduces or eliminates the damage of the SEI film caused by the deformation of the negative electrode material, reduces side reactions, reduces the expansion force of the cell, improves the life of the cell and improves safety performance, thereby The above problems are effectively solved.
  • the above-mentioned alkali metal oxide may be selected from Na 6 FeO 4 , K 6 FeO 4 , Na 6 CoO 4 , K 6 CoO 4 , Li 2 Na 4 FeO 4 and Li 2 K 4 FeO 4 at least one.
  • Na ions and/or K ions can be used to reliably expand the negative electrode material, thereby obtaining the above-mentioned technical effects.
  • the content of the alkali metal oxide is 0.1% to 10% by weight, preferably 0.5% to 4% by weight relative to the total 100% by weight of the positive electrode active material and the alkali metal oxide.
  • the proportion of alkali metal oxide is lower than 0.1wt%, Na and K ions are less intercalated into the negative electrode, and the negative electrode material cannot be stretched well, and the improvement effect on cycle and expansion is small.
  • the proportion of alkali metal oxide is higher than 10wt%, a large amount of Na and K ions are embedded in the negative electrode, resulting in a large initial expansion of the negative electrode, leaving more space inside the cell to absorb the expansion, resulting in a decrease in energy density.
  • the positive electrode of the lithium ion secondary battery of the present application includes the above-mentioned positive electrode composite material for lithium ion secondary batteries.
  • the present application is not limited to the composition that the above-mentioned alkali metal oxide is included in the positive electrode composite material together with the positive electrode active material to form the positive electrode.
  • the above-mentioned alkali metal oxide can also be used as an independent alkali metal oxide layer containing the alkali metal oxide,
  • the positive electrode is constituted together with the positive electrode current collector and the positive electrode active material layer containing the positive electrode active material.
  • the present application also provides a positive electrode of a lithium ion secondary battery, which includes: a positive electrode current collector, a positive electrode active material layer containing a positive electrode active material, and an alkali metal oxide layer containing an alkali metal oxide, the above-mentioned alkali metal
  • the oxide is represented by the formula AmGOn , wherein A represents at least one element selected from Na and K and optionally Li, and G represents an element selected from Fe, Ni, Co, Mn, Ru, Ir, Sn, Cr , at least one element among Nb, Mo, V and Ti, m is 1-6, and n is 1-4.
  • Na ions and/or K ions with larger ionic radii can also be used to open the negative electrode material, reducing or eliminating the lithium ions caused by repeated intercalation/extraction of lithium ions with smaller ionic radii in the negative electrode material.
  • the expansion/contraction deformation of the negative electrode material reduces or eliminates the damage of the SEI film caused by the deformation of the negative electrode material, reduces side reactions, and reduces the expansion force of the cell, thereby improving the life of the cell and improving safety performance.
  • the above-mentioned alkali metal oxide may be selected from Na 6 FeO 4 , K 6 FeO 4 , Na 6 CoO 4 , K 6 CoO 4 , Li 2 Na 4 FeO 4 and Li 2 K 4 FeO 4 at least one.
  • Na ions and/or K ions can be used to reliably expand the negative electrode material, thereby obtaining the above-mentioned technical effects.
  • the above-mentioned alkali metal oxide layer may be located between the above-mentioned positive electrode current collector and the above-mentioned positive electrode active material layer, or on the above-mentioned positive electrode active material layer.
  • the content of the above-mentioned alkali metal oxide is 0.1% by weight to 10% by weight, preferably 0.5% to 4% by weight.
  • the proportion of alkali metal oxide is lower than 0.1wt%, Na and K ions are less intercalated into the negative electrode, and the negative electrode material cannot be stretched well, and the improvement effect on cycle and expansion is small.
  • the proportion of alkali metal oxide is higher than 10wt%, a large amount of Na and K ions are embedded in the negative electrode, resulting in a large initial expansion of the negative electrode, leaving more space inside the cell to absorb the expansion, resulting in a decrease in energy density.
  • the lithium ion secondary battery of the present application includes a positive electrode containing the above-mentioned positive electrode composite material or a positive electrode having the above-mentioned layer structure, and a negative electrode.
  • the anode includes an anode active material
  • the anode active material includes at least one selected from carbon materials, metal or nonmetal compounds, coatings of the above compounds, and dopants of the above compounds.
  • the above-mentioned carbon material contains at least one selected from graphite, hard carbon and soft carbon
  • the above-mentioned metal or non-metallic compound contains oxides selected from silicon, selenium, sulfur, phosphorus, tin, titanium or vanadium.
  • the coating of the above compound includes: a coating obtained by coating the above metal or non-metal compound with graphite, soft carbon or hard carbon
  • the dopant of the above-mentioned compound includes: a dopant obtained by doping the above-mentioned metal or nonmetal compound with at least one element selected from Mg, Ni, Co, and Mn.
  • the metal or metalloid compound includes at least one selected from SiO 2 , SiO, SnO 2 , TiO 2 , SiS 2 and TiS 2 .
  • Na ions and/or K ions can be more reliably used to expand the negative electrode material, thereby obtaining the above technical effects.
  • the electric device of the present application includes the above-mentioned lithium ion secondary battery.
  • a lithium ion secondary battery is provided.
  • a lithium-ion secondary battery includes a positive pole piece, a negative pole piece, an electrolyte, and a separator.
  • the electrolyte plays the role of conducting ions between the positive pole piece and the negative pole piece.
  • the separator is set between the positive pole piece and the negative pole piece, which mainly plays a role in preventing the short circuit of the positive and negative poles, and at the same time allows ions to pass through.
  • the positive electrode sheet includes a positive electrode current collector and a positive electrode composite material layer disposed on at least one surface of the positive electrode current collector.
  • the positive electrode current collector has two opposing surfaces in its own thickness direction, and the positive electrode composite material layer is disposed on any one or both of the two opposing surfaces of the positive electrode current collector.
  • the above-mentioned positive electrode current collector may use a metal foil or a composite current collector.
  • aluminum foil can be used as the metal foil.
  • the composite current collector may include a polymer material base and a metal layer formed on at least one surface of the polymer material base.
  • the composite current collector can be formed by forming metal materials (aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as polypropylene (PP), polyethylene terephthalic acid It is formed on substrates such as ethylene glycol ester (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • PP polypropylene
  • PET polyethylene glycol ester
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the positive electrode composite material layer comprises the positive electrode active material and the alkali metal compound described in the formula AmGOn , wherein A represents at least one element selected from Na and K and optional Li , and G represents At least one element selected from Fe, Ni, Co, Mn, Ru, Ir, Sn, Cr, Nb, Mo, V and Ti, m is 1-6, and n is 1-4.
  • the positive electrode active material contained in the positive electrode composite material layer may be a positive electrode active material known in the art for batteries.
  • the positive electrode active material may be at least one selected from oxide-based positive electrode materials or polyanion-based positive electrode materials. These positive electrode active materials may be used alone or in combination of two or more.
  • olivine-type positive electrode materials such as LiMPO 4 (M is Fe, Co, Ni, Mn, etc.), Li 2 M 2 (PO 4 ) 3 (M is Fe, Co, Ni, Mn, etc.) , Ti, V, etc.) and other positive electrode materials with NASICON structure, or silicates such as Li 2 MSiO 4 (M is Fe, Mn).
  • the positive electrode composite material layer optionally further includes a binder.
  • the above binder may include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene At least one of terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and fluorine-containing acrylate resin.
  • the positive electrode composite material layer optionally further includes a conductive agent.
  • the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
  • the positive electrode sheet can be prepared by dispersing, for example, positive electrode active material and alkali metal oxide, conductive agent, binder and any other components in a solvent (such as N-methylpyrrolidone) In the process, the positive electrode slurry is formed; the positive electrode slurry is coated on the positive electrode current collector, and after drying, cold pressing and other processes, the positive electrode sheet can be obtained.
  • a solvent such as N-methylpyrrolidone
  • the positive electrode sheet includes a positive electrode current collector, a positive electrode active material layer disposed on at least one surface of the positive electrode current collector, and a positive electrode active material layer between the positive electrode current collector and the positive electrode active material layer or on the positive electrode active material layer.
  • Alkali metal oxide layer The alkali metal oxide shown in the above alkali metal oxide formula A m GO n , wherein, A represents at least one element selected from Na and K and optional Li, and G represents an element selected from Fe, Ni, Co, Mn , at least one element among Ru, Ir, Sn, Cr, Nb, Mo, V and Ti, m is 1-6, and n is 1-4.
  • the positive electrode current collector, the alkali metal oxide, and the positive electrode active material may be the same as those in the above embodiments, and repeated descriptions are omitted here.
  • the positive electrode active material layer and the alkali metal oxide layer optionally further include a binder.
  • the above binder may include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene At least one of terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and fluorine-containing acrylate resin.
  • the positive electrode active material layer and the alkali metal oxide layer optionally further include a conductive agent.
  • the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
  • the positive electrode sheet can be prepared by dispersing, for example, positive electrode active materials, conductive agents, binders and any other components in a solvent (such as N-methylpyrrolidone) to form a positive electrode active Material slurry; the positive electrode active material slurry is coated on the positive electrode current collector, and the positive electrode active material layer is obtained through drying, cold pressing and other processes; for example, alkali metal oxides, conductive agents, binders and any other components Dispersed in a solvent (such as N-methylpyrrolidone) to form an alkali metal oxide slurry; then coat the alkali metal oxide slurry on the obtained positive electrode active material layer, and after drying, cold pressing and other processes , the positive electrode sheet can be obtained.
  • a solvent such as N-methylpyrrolidone
  • the alkali metal oxide slurry obtained above can be coated on the positive electrode current collector, and the alkali metal oxide layer can be obtained through drying, cold pressing and other processes;
  • the positive electrode active material slurry obtained above is coated on the layer, and after drying, cold pressing and other processes, a positive electrode sheet is obtained.
  • the negative electrode sheet includes a negative electrode current collector and a negative electrode material layer arranged on at least one surface of the negative electrode current collector.
  • the negative electrode current collector has two opposing surfaces in its own thickness direction, and the negative electrode material layer is disposed on any one or both of the two opposing surfaces of the negative electrode current collector.
  • the above-mentioned negative electrode current collector may use a metal foil or a composite current collector.
  • copper foil can be used as the metal foil.
  • the composite current collector may include a base layer of polymer material and a metal layer formed on at least one surface of the base material of polymer material.
  • Composite current collectors can be formed by metal materials (copper, copper alloys, nickel, nickel alloys, titanium, titanium alloys, silver and silver alloys, etc.) on polymer material substrates (such as polypropylene (PP), polyethylene terephthalic acid It is formed on substrates such as ethylene glycol ester (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • negative electrode active materials known in the art for batteries can be used in the negative electrode material layer.
  • the negative electrode active material may include at least one of the following materials: carbon materials, metal or non-metal compounds, coatings of the above compounds, dopants of the above compounds, and the like.
  • the above-mentioned carbon material comprises at least one selected from graphite, hard carbon and soft carbon
  • the above-mentioned metal or metalloid compound comprises oxides, sulfides, selenium selected from silicon, selenium, sulfur, phosphorus, tin, titanium or vanadium
  • the coating of the above compound includes: the coating obtained by coating the above metal or non-metal compound with graphite, soft carbon or hard carbon
  • the dopant of the above compound Contains: a dopant obtained by doping the above-mentioned metal or nonmetal compound with at least one element selected from Mg, Ni, Co, and Mn.
  • the metal or metalloid compound includes at least one selected from SiO 2 , SiO, SnO 2 , TiO 2 , SiS 2 and TiS 2 .
  • the present application is not limited to these materials, and other conventional materials that can be used as negative electrode active materials of batteries can also be used. These negative electrode active materials may be used alone or in combination of two or more.
  • the negative electrode material layer may further optionally include a binder.
  • the above binder can be selected from styrene-butadiene rubber (SBR), polyacrylic acid (PAA), sodium polyacrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), polyformaldehyde At least one of polyacrylic acid (PMAA) and carboxymethyl chitosan (CMCS).
  • the negative electrode material layer optionally further includes a conductive agent.
  • the conductive agent can be selected from at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
  • the negative electrode material layer may optionally include other additives, such as thickeners (such as sodium carboxymethylcellulose (CMC-Na)) and the like.
  • thickeners such as sodium carboxymethylcellulose (CMC-Na)
  • a dispersant may also be used when preparing the negative electrode material layer.
  • the dispersant is used to improve dispersion uniformity and coating property, and may be a dispersant commonly used in the battery field, such as a polymer dispersant.
  • polyvinyl alcohol modified polyvinyl alcohol having functional groups other than hydroxyl group such as acetyl group, sulfo group, carboxyl group, carbonyl group, amino group, modified by various salts, others modified by anion or cation, by Acetal-modified polyvinyl alcohol-based resins, various (meth)acrylic polymers, polymers derived from ethylenically unsaturated hydrocarbons, various cellulose-based resins, etc., or copolymers of these , but are not limited to these.
  • the polymer dispersants may be used alone or in combination of two or more.
  • the negative electrode sheet can be prepared in the following manner: the above-mentioned components used to prepare the negative electrode sheet, such as negative electrode active material, conductive agent, binder and any other components, are dispersed in a solvent (such as deionized water) to form a negative electrode slurry; the negative electrode slurry is coated on the negative electrode current collector, and after drying, cold pressing and other processes, the negative electrode sheet can be obtained.
  • a solvent such as deionized water
  • the electrolyte plays the role of conducting ions between the positive pole piece and the negative pole piece.
  • the present application has no specific limitation on the type of electrolyte, which can be selected according to requirements.
  • electrolytes can be liquid, gel or all solid.
  • the above-mentioned electrolyte is an electrolytic solution.
  • the above electrolytic solution includes electrolyte salt and solvent.
  • the electrolyte salt may be selected from lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bisfluorosulfonyl imide, lithium bistrifluoromethanesulfonyl imide, trifluoromethane At least one of lithium sulfonate, lithium difluorophosphate, lithium difluorooxalate borate, lithium difluorooxalate borate, lithium difluorodifluorooxalatephosphate and lithium tetrafluorooxalatephosphate.
  • the solvent may be selected from ethylene carbonate, propylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, Butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate At least one of ester, 1,4-butyrolactone, sulfolane, dimethyl sulfone, methyl ethyl sulfone and diethyl sulfone.
  • the above electrolytic solution may optionally include additives.
  • additives may include negative electrode film-forming additives, positive electrode film-forming additives, and additives that can improve certain performances of the battery, such as additives that improve battery overcharge performance, additives that improve high-temperature or low-temperature performance of batteries, and the like.
  • the lithium-ion secondary battery also includes a separator.
  • a separator There is no particular limitation on the type of the separator in the present application, and any known porous structure separator with good chemical stability and mechanical stability can be selected.
  • the material of the isolation film can be selected from at least one of glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride.
  • the separator can be a single-layer film or a multi-layer composite film, without any particular limitation. When the separator is a multilayer composite film, the materials of each layer may be the same or different, and there is no particular limitation.
  • the positive pole piece, the negative pole piece and the separator can be made into an electrode assembly through a winding process or a lamination process.
  • a lithium ion secondary battery may include an outer package.
  • the outer package can be used to package the above-mentioned electrode assembly and electrolyte.
  • the outer package of the lithium-ion secondary battery may be a hard case, such as a hard plastic case, aluminum case, steel case, and the like.
  • the outer packaging of the lithium-ion secondary battery may also be a soft bag, such as a pouch-type soft bag.
  • the material of the soft case may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, polybutylene succinate, and the like.
  • FIG. 1 shows a square-shaped lithium-ion secondary battery 5 as an example.
  • the outer package may include a housing 51 and a cover 53 .
  • the housing 51 may include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plates enclose to form an accommodating cavity.
  • the housing 51 has an opening communicating with the accommodating chamber, and the cover plate 53 can cover the aforesaid opening to close the aforesaid accommodating chamber.
  • the positive pole piece, the negative pole piece and the separator can be formed into an electrode assembly 52 through a winding process or a lamination process.
  • the electrode assembly 52 is packaged in the aforesaid cavity. Electrolyte is infiltrated in the electrode assembly 52 .
  • the number of electrode assemblies 52 contained in the lithium-ion secondary battery 5 can be one or more, and those skilled in the art can select according to specific actual needs.
  • the lithium-ion secondary battery can be assembled into a battery module, and the number of lithium-ion secondary batteries contained in the battery module can be one or more, and the specific number can be determined by those skilled in the art according to the application and capacity of the battery module. choose.
  • FIG. 3 is a battery module 4 as an example.
  • a plurality of secondary batteries 5 may be arranged in sequence along the length direction of the battery module 4 .
  • the plurality of secondary batteries 5 may be fixed by fasteners.
  • the battery module 4 may also include a case having a housing space in which a plurality of secondary batteries 5 are accommodated.
  • the above-mentioned battery modules can also be assembled into a battery pack, and the number of battery modules contained in the battery pack can be one or more, and the specific number can be selected by those skilled in the art according to the application and capacity of the battery pack.
  • the battery pack 1 may include a battery box and a plurality of battery modules 4 disposed in the battery box.
  • the battery box includes an upper box body 2 and a lower box body 3 , the upper box body 2 can cover the lower box body 3 and form a closed space for accommodating the battery module 4 .
  • Multiple battery modules 4 can be arranged in the battery box in any manner.
  • the present application also provides an electric device, which includes the lithium-ion secondary battery provided in the present application.
  • the above-mentioned lithium-ion secondary battery can be used as a power source of the above-mentioned electric device, and can also be used as an energy storage unit of the above-mentioned electric device.
  • the aforementioned electrical devices may include mobile devices (such as mobile phones, laptop computers, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, Electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but not limited thereto.
  • a lithium-ion secondary battery, a battery module, or a battery pack can be selected according to its use requirements.
  • FIG. 6 is an example of an electrical device.
  • the electric device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle.
  • a battery pack or a battery module may be used.
  • a device may be a cell phone, tablet, laptop, or the like.
  • the device is usually required to be light and thin, and a lithium-ion secondary battery can be used as a power source.
  • NMP N-methyl-pyrrolidone
  • the slurry was coated on a positive electrode current collector using a coater. After drying at 85°C, carry out cold pressing, then trim, cut into pieces, and slitting, and then dry at 85°C for 4 hours under vacuum conditions, and weld the tabs to make positive pole pieces of secondary batteries that meet the requirements.
  • the preparation of the negative electrode sheet of the secondary battery the negative electrode active material graphite, the conductive agent Super-P, the thickener CMC, and the adhesive SBR are added to the solvent deionized water according to the mass ratio of 96.5:1.0:1.0:1.5 and mixed evenly to prepare To form negative electrode slurry; apply the negative electrode slurry on the copper foil of the current collector and dry it at 85°C, then trim, cut into pieces, and divide into strips, and then dry it under vacuum at 110°C for 4 hours, and then weld the electrode Ears are made into negative pole pieces of secondary batteries that meet the requirements.
  • EC ethylene carbonate
  • PC propylene carbonate
  • DEC diethyl carbonate
  • Preparation of secondary battery Use 12 ⁇ m polypropylene film as the separator, stack the positive electrode, separator, and negative electrode in order, so that the separator is in the middle of the positive and negative electrodes to play the role of isolation, and then roll Wind a square bare cell with a thickness of 8mm, a width of 60mm, and a length of 130mm.
  • the preparation of the positive electrode sheet of the secondary battery the positive electrode active material LiNi 0.5 Co 0.2 Mn 0.3 O 2 , alkali metal oxide K 6 FeO 4 , polyvinylidene fluoride (PVDF), conductive agent (carbon black Super P) by mass Mix at a ratio of 89:1:5:5, use N-methyl-pyrrolidone (NMP) as a solvent, adjust the amount of solvent added, and control the viscosity of the slurry at 3000-20000mPa.s.
  • NMP N-methyl-pyrrolidone
  • the slurry was coated on a positive electrode current collector using a spray coater. After drying at 85°C, carry out cold pressing, then trim, cut into pieces, and slitting, and then dry at 85°C for 4 hours under vacuum conditions, and weld the tabs to make positive pole pieces of secondary batteries that meet the requirements.
  • the preparation of the negative electrode sheet of the secondary battery the negative electrode active material graphite, the conductive agent Super-P, the thickener CMC, and the adhesive SBR are added to the solvent deionized water according to the mass ratio of 96.5:1.0:1.0:1.5 and mixed evenly to prepare To form negative electrode slurry; apply the negative electrode slurry on the copper foil of the current collector and dry it at 85°C, then trim, cut into pieces, and divide into strips, and then dry it under vacuum at 110°C for 4 hours, and then weld the electrode Ears are made into negative pole pieces of secondary batteries that meet the requirements.
  • EC ethylene carbonate
  • PC propylene carbonate
  • DEC diethyl carbonate
  • Preparation of the secondary battery use 12 ⁇ m polypropylene film as the separator, stack the positive pole piece, separator film and negative pole piece in order, so that the separator film is in the middle of the positive and negative pole piece to play the role of isolation, and then roll Wind a square bare cell with a thickness of 8mm, a width of 60mm, and a length of 130mm.
  • the preparation of the positive electrode sheet of the secondary battery the positive electrode active material LiNi 0.5 Co 0.2 Mn 0.3 O 2 , alkali metal oxide Li 2 Na 4 FeO 4 , polyvinylidene fluoride (PVDF), conductive agent (carbon black Super P) Mix according to the mass ratio of 87.5:2.5:5:5, use N-methyl-pyrrolidone (NMP) as the solvent, adjust the amount of solvent added, and control the viscosity of the slurry at 3000-20000mPa.s.
  • NMP N-methyl-pyrrolidone
  • the slurry was coated on a positive electrode current collector using a coater. After drying at 85°C, carry out cold pressing, then trim, cut into pieces, and slitting, and then dry at 85°C for 4 hours under vacuum conditions, and weld the tabs to make positive pole pieces of secondary batteries that meet the requirements.
  • the preparation of the negative electrode sheet of the secondary battery the negative electrode active material graphite, the conductive agent Super-P, the thickener CMC, and the adhesive SBR are added to the solvent deionized water according to the mass ratio of 96.5:1.0:1.0:1.5 and mixed evenly to prepare To form negative electrode slurry; apply the negative electrode slurry on the copper foil of the current collector and dry it at 85°C, then trim, cut into pieces, and divide into strips, and then dry it under vacuum at 110°C for 4 hours, and then weld the electrode Ears are made into negative pole pieces of secondary batteries that meet the requirements.
  • EC ethylene carbonate
  • PC propylene carbonate
  • DEC diethyl carbonate
  • Preparation of secondary battery Use 12 ⁇ m polypropylene film as the separator, stack the positive electrode, separator, and negative electrode in order, so that the separator is in the middle of the positive and negative electrodes to play the role of isolation, and then roll Wind a square bare cell with a thickness of 8mm, a width of 60mm, and a length of 130mm.
  • Preparation of the positive electrode sheet of the secondary battery the same operation as in Example 2 was performed to prepare the positive electrode sheet of the secondary battery.
  • Preparation of the negative electrode sheet of the secondary battery mix SiO in graphite to obtain a mixture, wherein the amount of SiO is 25% by mass relative to the above-mentioned mixture as a whole, and the obtained mixture is used as the negative electrode active material, and the negative electrode active material, the conductive agent Super -P, thickener CMC, and binder SBR are added to the solvent deionized water at a mass ratio of 96.5:1.0:1.0:1.5 and mixed evenly to prepare negative electrode slurry.
  • the same operations as in Example 2 were carried out to manufacture negative electrode sheets for secondary batteries.
  • Preparation of the positive electrode sheet of the secondary battery the same operation as in Example 2 was performed to prepare the positive electrode sheet of the secondary battery.
  • Preparation of the negative pole sheet of the secondary battery mix the SiO carbon coating in the graphite to obtain the mixture, wherein the amount of the SiO carbon coating is 25% by mass relative to the above-mentioned mixture, and use the mixture as the negative electrode active material, and the negative electrode
  • the active material, the conductive agent Super-P, the thickener CMC, and the binder SBR are added to the solvent deionized water at a mass ratio of 96.5:1.0:1.0:1.5 and mixed evenly to form a negative electrode slurry.
  • the same operation as in Example 2 was carried out to produce a secondary battery negative electrode sheet.
  • Embodiment 6 is a diagrammatic representation of Embodiment 6
  • Preparation of the positive electrode sheet of the secondary battery the same operation as in Example 2 was performed to prepare the positive electrode sheet of the secondary battery.
  • the preparation of the negative pole sheet of the secondary battery mixing the dopant obtained by doping SiO with magnesium in graphite (wherein, the amount of magnesium relative to the SiO magnesium dopant as a whole is 0.1% to 2%), to obtain The mixture, wherein the amount of SiO magnesium dopant is 25% by mass relative to the above-mentioned mixture, the mixture is used as the negative electrode active material, and the negative electrode active material, the conductive agent Super-P, the thickener CMC, and the binder SBR are The ratio 96.5:1.0:1.0:1.5 was added to the solvent deionized water and mixed evenly to make negative electrode slurry. Other than that, the same operation as in Example 2 was carried out to produce a secondary battery negative electrode sheet.
  • Embodiment 7 is a diagrammatic representation of Embodiment 7:
  • the preparation of the positive electrode sheet of the secondary battery the positive electrode active material LiNi 0.5 Co 0.2 Mn 0.3 O 2 , alkali metal oxide K 6 FeO 4 , polyvinylidene fluoride (PVDF), conductive agent (carbon black Super P) by mass
  • PVDF polyvinylidene fluoride
  • carbon black Super P carbon black Super P
  • Embodiment 8 is a diagrammatic representation of Embodiment 8
  • the preparation of the positive electrode sheet of the secondary battery the positive electrode active material LiNi 0.5 Co 0.2 Mn 0.3 O 2 , alkali metal oxide K 6 FeO 4 , polyvinylidene fluoride (PVDF), conductive agent (carbon black Super P) by mass
  • the mixture was mixed at a ratio of 89.55:0.45:5:5, except that, the same operation as in Example 2 was performed to make a secondary battery positive electrode sheet.
  • Embodiment 9 is a diagrammatic representation of Embodiment 9:
  • the preparation of the positive electrode sheet of the secondary battery the positive electrode active material LiNi 0.5 Co 0.2 Mn 0.3 O 2 , alkali metal oxide K 6 FeO 4 , polyvinylidene fluoride (PVDF), conductive agent (carbon black Super P) by mass
  • PVDF polyvinylidene fluoride
  • carbon black Super P carbon black Super P
  • the preparation of the positive electrode sheet of the secondary battery the positive electrode active material LiNi 0.5 Co 0.2 Mn 0.3 O 2 , alkali metal oxide K 6 FeO 4 , polyvinylidene fluoride (PVDF), conductive agent (carbon black Super P) by mass
  • PVDF polyvinylidene fluoride
  • carbon black Super P conductive agent
  • the preparation of the positive electrode sheet of the secondary battery the positive electrode active material LiNi 0.5 Co 0.2 Mn 0.3 O 2 , alkali metal oxide K 6 FeO 4 , polyvinylidene fluoride (PVDF), conductive agent (carbon black Super P) by mass
  • PVDF polyvinylidene fluoride
  • carbon black Super P conductive agent
  • the preparation of the positive electrode sheet of the secondary battery the positive electrode active material LiNi 0.5 Co 0.2 Mn 0.3 O 2 , alkali metal oxide K 6 FeO 4 , polyvinylidene fluoride (PVDF), conductive agent (carbon black Super P) by mass
  • the mixture was mixed at a ratio of 80.1:9.9:5:5, except that, the same operation was performed as in Example 2 to make a secondary battery positive electrode sheet.
  • the alkali metal oxide Na 6 FeO 4 is mixed with polyvinylidene fluoride (PVDF), a conductive agent (carbon black Super P), and N-methyl-pyrrolidone (NMP) is used as a solvent. Adjust the amount of solvent added so that the viscosity of the slurry is controlled at 3000-20000mPa.s. This slurry was coated on a positive electrode current collector using a coater to form an alkali metal oxide layer.
  • PVDF polyvinylidene fluoride
  • NMP N-methyl-pyrrolidone
  • the positive electrode active material LiNi 0.5 Co 0.2 Mn 0.3 O 2 is mixed with polyvinylidene fluoride (PVDF) and conductive agent (carbon black Super P), so that LiNi 0.5 Co 0.2 Mn 0.3 O 2 is coated on the positive electrode current collector.
  • PVDF polyvinylidene fluoride
  • conductive agent carbon black Super P
  • the mass ratio of the alkali metal oxide Na 6 FeO 4 is 88:2, N-methyl-pyrrolidone (NMP) is used as the solvent, and the amount of the solvent is adjusted to control the viscosity of the slurry at 3000-20000mPa.s. This slurry was coated on the alkali metal oxide layer using a coater.
  • the positive electrode active material LiNi 0.5 Co 0.2 Mn 0.3 O 2 mixed with polyvinylidene fluoride (PVDF), conductive agent (carbon black Super P), N methyl-pyrrolidone (NMP) is Solvent, adjust the amount of solvent added, so that the viscosity of the slurry is controlled at 3000-20000mPa.s.
  • the slurry was coated on a positive electrode current collector using a coater to form a positive electrode active material layer.
  • the positive electrode active material LiNi 0.5 Co 0.2 Mn 0.3 O 2 , alkali metal oxide Na 6 CoO 4 , polyvinylidene fluoride (PVDF), conductive agent (carbon black Super P) by mass The mixture was mixed at a ratio of 88:2:5:5, except that, the same operation was performed as in Example 1 to make a secondary battery positive electrode sheet.
  • the preparation of the positive electrode sheet of the secondary battery the positive electrode active material LiNi 0.5 Co 0.2 Mn 0.3 O 2 , polyvinylidene fluoride (PVDF), conductive agent (carbon black Super P) are mixed in a mass ratio of 90:5:5, and N-methyl-pyrrolidone (NMP) is used as a solvent, and the addition amount of the solvent is adjusted so that the viscosity of the slurry is controlled at 3000-20000mPa.s.
  • NMP N-methyl-pyrrolidone
  • the slurry was coated on a positive electrode current collector using a coater. After drying at 85°C, carry out cold pressing, then trim, cut into pieces, and slitting, and then dry at 85°C for 4 hours under vacuum conditions, and weld the tabs to make positive pole pieces of secondary batteries that meet the requirements.
  • the preparation of the negative electrode sheet of the secondary battery the negative electrode active material graphite, the conductive agent Super-P, the thickener CMC, and the adhesive SBR are added to the solvent deionized water according to the mass ratio of 96.5:1.0:1.0:1.5 and mixed evenly to prepare To form negative electrode slurry; apply the negative electrode slurry on the copper foil of the current collector and dry it at 85°C, then trim, cut into pieces, and divide into strips, and then dry it under vacuum at 110°C for 4 hours, and then weld the electrode Ears are made into negative pole pieces of secondary batteries that meet the requirements.
  • EC ethylene carbonate
  • PC propylene carbonate
  • DEC diethyl carbonate
  • Preparation of secondary battery Use 12 ⁇ m polypropylene film as the separator, stack the positive electrode, separator, and negative electrode in order, so that the separator is in the middle of the positive and negative electrodes to play the role of isolation, and then roll Wind a square bare cell with a thickness of 8mm, a width of 60mm, and a length of 130mm.
  • the preparation of the positive electrode sheet of the secondary battery the positive electrode active material LiNi 0.5 Co 0.2 Mn 0.3 O 2 , polyvinylidene fluoride (PVDF), conductive agent (carbon black Super P) are mixed in a mass ratio of 90:5:5, and N-methyl-pyrrolidone (NMP) is used as a solvent, and the addition amount of the solvent is adjusted so that the viscosity of the slurry is controlled at 3000-20000mPa.s.
  • NMP N-methyl-pyrrolidone
  • the slurry was coated on a positive electrode current collector using a coater. After drying at 85°C, carry out cold pressing, then trim, cut into pieces, and slitting, and then dry at 85°C for 4 hours under vacuum conditions, and weld the tabs to make positive pole pieces of secondary batteries that meet the requirements.
  • Preparation of the negative electrode sheet of the secondary battery mix SiO in graphite to obtain a mixture, wherein the amount of SiO is 25% by mass relative to the above-mentioned mixture as a whole, and the obtained mixture is used as the negative electrode active material, and the negative electrode active material, the conductive agent Super -P, thickener CMC, and binder SBR are added to the solvent deionized water at a mass ratio of 96.5:1.0:1.0:1.5 and mixed evenly to prepare negative electrode slurry.
  • the same operations as in Example 2 were carried out to manufacture negative electrode sheets for secondary batteries.
  • EC ethylene carbonate
  • PC propylene carbonate
  • DEC diethyl carbonate
  • Preparation of secondary battery Use 12 ⁇ m polypropylene film as the separator, stack the positive electrode, separator, and negative electrode in order, so that the separator is in the middle of the positive and negative electrodes to play the role of isolation, and then roll Wind a square bare cell with a thickness of 8mm, a width of 60mm, and a length of 130mm.
  • the 1C/1C cycle test was carried out on the secondary batteries of the above-mentioned Examples 1-15 and Comparative Examples 1-2.
  • the charge-discharge voltage range was 2.8-4.5V, and the capacity decayed to 80% of the specific capacity of the first discharge. Stop the test and record the number of cycles and expansion force.
  • the positive electrode composite material used to form the positive electrode contains an alkali metal oxide, or the positive electrode includes an alkali metal oxide layer formed of an alkali metal oxide, and the expansion force of the cell is obtained. Low energy consumption, high cycle life, and excellent energy density.
  • the present application is not limited to the above-mentioned embodiments.
  • the above-mentioned embodiments are merely examples, and within the scope of the technical solution of the present application, embodiments that have substantially the same configuration as the technical idea and exert the same function and effect are included in the technical scope of the present application.
  • various modifications conceivable by those skilled in the art are added to the embodiments, and other forms constructed by combining some components in the embodiments are also included in the scope of the present application. .

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Abstract

本申请提供了一种用于锂离子二次电池的正极复合材料、以及使用了该正极复合材料的锂离子二次电池的正极、锂离子二次电池和用电装置。该用于锂离子二次电池的正极复合材料包含正极活性材料和式A mGO n所示的碱金属氧化物，其中，A代表选自Na和K中的至少一种元素和任选的Li，G代表选自Fe、Ni、Co、Mn、Ru、Ir、Sn、Cr、Nb、Mo、V和Ti中的至少一种元素，m为1～6，且n为1～4。

Description

一种用于锂离子二次电池的正极复合材料、正极和电池 技术领域
本申请涉及电池领域，尤其涉及一种用于锂离子二次电池的正极复合材料、以及使用了该正极复合材料的锂离子二次电池的正极、锂离子二次电池和用电装置。
背景技术
近年来，随着锂离子二次电池的应用范围越来越广泛，锂离子二次电池被广泛应用于水力、火力、风力和太阳能电站等储能电源系统，以及电动工具、电动自行车、电动摩托车、电动汽车、军事装备、航空航天等多个领域。由于锂离子二次电池取得了极大的发展，因此对其能量密度、循环性能、电芯寿命和安全性能等也提出了更高的要求。
锂离子二次电池主要依靠锂离子在正极和负极之间移动来工作。在充放电过程中，锂离子在两个电极之间往返嵌入和脱出，充电时锂离子从正极脱出，经过电解质嵌入负极，负极处于富锂状态，放电时则相反。
基于锂离子二次电池的这种工作机理，在使用过程中，负极材料(例如石墨)在充放电期间随着锂离子的嵌入/脱出而不断发生膨胀/收缩，造成固体电解质界面膜(以下有时简称为SEI膜)不断破坏/修复，导致副产物不断增厚引起膨胀。负极材料随锂离子的嵌入/脱出而不断膨胀/收缩会造成颗粒间粘结力降低，导致颗粒重排引起负极厚度增长，导致锂离子二次电池在使用过程中膨胀力不断增加。一旦这种膨胀力超过化学体系膨胀力阈值，就会导致电芯循环衰减加速，无法满足质保要求甚至发生热失控。因此，现有的电池结构仍有待改进。
发明内容
本申请是鉴于上述问题而进行的，其目的在于提供一种能够减小或消除负极材料变形引起的SEI膜破坏、降低副反应、降低电芯膨胀力、从而改善电芯寿命并提升安全性能的用于锂离子二次电池的正极复合材料。
为了实现上述目的，本申请的第一方面提供了一种用于锂离子二次电池的正极复合材料，其包含正极活性材料和式A mGO n所示的碱金属氧化物，其中，A代表选自Na和K中的至少一种元素和任选的Li，G代表选自Fe、Ni、Co、Mn、Ru、Ir、Sn、Cr、Nb、Mo、V和Ti中的至少一种元素，m为1～6，且n为1～4。
通过正极复合材料中包含上述A mGO n所示的碱金属氧化物，利用离子半径较大的Na离子和/或K离子撑开负极材料，减小或消除因离子半径较小的锂离子在负极材料中反复嵌入/脱出而引起的负极材料的膨胀/收缩变形，减小或消除负极材料变形引起的SEI膜破坏，降低副反应，降低电芯膨胀力，从而改善电芯寿命并提升安全性能。
在任意实施方式中，上述碱金属氧化物为选自Na 6FeO 4、K 6FeO 4、Na 6CoO 4、K 6CoO 4、Li 2Na 4FeO 4和Li 2K 4FeO 4中的至少一种。通过使用这些化合物作为上述A mGO n所示的碱金属氧化物，能够更可靠地利用Na离子和/或K离子撑开负极材料，从而获得上述技术效果。
在任意实施方式中，相对于总计100重量％的上述正极活性材料和上述碱金属氧化物，上述碱金属氧化物的含量为0.1重量％～10重量％，优选为0.5重量％～4重量％。通过碱金属氧化物高于0.1wt％，能够使充分量的Na、K等离子嵌入负极，很好地撑开负极材料，对循环和膨胀的改善效果优异。并且，通过碱金属氧化物低于10wt％，不会因大量Na、K等离子嵌入负极而造成负极初始膨胀大，电芯内部不会留存较多空间来吸收膨胀，因而电池的能量密度高。
本申请的第二方面还提供了一种锂离子二次电池的正极，其包括本申请的第一方面的用于锂离子二次电池的正极复合材料。通过本申请，能够提供具有高能量密度、高电芯寿命和高安全性能的锂离子二次电池。
本申请的第三方面还提供了一种锂离子二次电池的正极，其包括：正极集流体、包含正极活性材料的正极活性材料层、和包含碱金属氧化物的碱金属氧化物层，上述碱金属氧化物由式A mGO n表示，其中，A代表选自Na和K中的至少一种元素和任选的Li，G代表选自Fe、Ni、Co、Mn、Ru、Ir、Sn、Cr、Nb、Mo、V和Ti中的至少一种元素，m为1～6，且n为1～4。
通过正极包括包含上述碱金属氧化物的碱金属氧化物层，能够利用离子半径较大的Na离子和/或K离子撑开负极材料，减小或消除因离子半径较小的锂离子在负极材料中反复嵌入/脱出而引起的负极材料的膨胀/收缩变形，减小或消除负极材料变形引起的SEI膜破坏，降低副反应，降低电芯膨胀力，从而改善电芯寿命并提升安全性能。
在任意实施方式中，上述碱金属氧化物为选自Na 6FeO 4、K 6FeO 4、Na 6CoO 4、K 6CoO 4、Li 2Na 4FeO 4和Li 2K 4FeO 4中的至少一种。通过使用这些化合物作为上述A mGO n所示的碱金属氧化物，能够更可靠地利用Na离子和/或K离子撑开负极材料，从而获得上述技术效果。
在任意实施方式中，上述碱金属氧化物层位于上述正极集流体与上述正极活性材料层之间、或者上述正极活性材料层之上。通过设置为这样的层结构，能够很好地获得上述技术效果并且不会阻碍锂离子在正极与负极之间的移动。
在任意实施方式中，相对于总计100重量％的上述正极活性材料层所含的正极活性材料和上述碱金属氧化物层所含的碱金属氧化物，上述碱金属氧化物的含量为0.1重量％～10重量％，优选为0.5重量％～4重量％。通过碱金属氧化物高于0.1wt％，能够使充分量的Na、K等离子嵌入负极，很好地撑开负极材料，对循环和膨胀的改善效果优异。并且，通过碱金属氧化物低于10wt％，不会因大量Na、K等离子嵌入负极而造成负极初始膨胀增大，电芯内部不会留存较多空间来吸收膨胀，因而电池的能量密度高。
本申请的第四方面还提供了一种锂离子二次电池，其包括本申请的第二方面或第三方面的正极，并且包括负极。
在任意实施方式中，上述负极包含负极活性材料，上述负极活性材料包含选自碳材料、金属或非金属的化合物以及上述化合物的包覆物和上述化合物的掺杂物中的至少一种。通过使用这些物质作为锂离子二次电池的负极活性材料，能够可靠地利用碱金属氧化物所包含的Na离子和/或K离子撑开负极材料，从而获得上述技术效果。
在任意实施方式中，上述碳材料包含选自石墨、硬碳和软碳中的至少一种，上述金属或非金属的化合物包含选自硅、硒、硫、磷、锡、钛或钒的氧化物、硫化物、硒化物和氟化物中的至少一种，上述化合 物的包覆物包含：用石墨、软碳或硬碳对上述金属或非金属的化合物进行包覆而得到的包覆物，上述化合物的掺杂物包含：用选自Mg、Ni、Co、Mn中的至少一种元素对上述金属或非金属的化合物进行掺杂而得到的掺杂物。通过使用这些物质作为锂离子二次电池的负极活性材料，能够更可靠地利用Na离子和/或K离子撑开负极材料，从而获得上述技术效果。
在任意实施方式中，上述金属或非金属的化合物包含选自SiO 2、SiO、SnO 2、TiO 2、SiS 2和TiS 2中的至少一种。通过使用这些物质作为锂离子二次电池的负极活性材料，能够更可靠地利用Na离子和/或K离子撑开负极材料，从而获得上述技术效果。
本申请的第五方面还提供了一种用电装置，其包括本申请的第四方面的二次电池。由于用电装置包括上述的二次电池，因而具有该二次电池的所有有益效果。
附图说明
图1是本申请一实施方式的二次电池的示意图。
图2是图1所示的本申请一实施方式的二次电池的分解图。
图3是本申请一实施方式的电池模块的示意图。
图4是本申请一实施方式的电池包的示意图。
图5是图4所示的本申请一实施方式的电池包的分解图。
图6是本申请一实施方式的二次电池用作电源的用电装置的示意图。
附图标记说明：
1：电池包；2：上箱体；3：下箱体；4：电池模块；5：二次电池；51：壳体；52：电极组件；53：顶盖组件。
具体实施方式
以下，适当地参照附图详细说明具体公开了本申请的用于锂离子二次电池的正极复合材料、以及使用了该正极复合材料的锂离子二次电池的正极、锂离子二次电池和用电装置的实施方式。但是会有省略 不必要的详细说明的情况。例如，有省略对已众所周知的事项的详细说明、实际相同结构的重复说明的情况。这是为了避免以下的说明不必要地变得冗长，便于本领域技术人员的理解。此外，附图及以下说明是为了本领域技术人员充分理解本申请而提供的，并不旨在限定权利要求书所记载的主题。
本申请所公开的“范围”以下限和上限的形式来限定，给定范围是通过选定一个下限和一个上限进行限定的，选定的下限和上限限定了特别范围的边界。这种方式进行限定的范围可以是包括端值或不包括端值的，并且可以进行任意地组合，即任何下限可以与任何上限组合形成一个范围。例如，如果针对特定参数列出了60～120和80～110的范围，理解为60～110和80～120的范围也是预料到的。此外，如果列出的最小范围值1和2，和如果列出了最大范围值3，4和5，则下面的范围可全部预料到：1～3、1～4、1～5、2～3、2～4和2～5。在本申请中，除非有其他说明，数值范围“a～b”表示a到b之间的任意实数组合的缩略表示，其中a和b都是实数。例如数值范围“0～5”表示本文中已经全部列出了“0～5”之间的全部实数，“0～5”只是这些数值组合的缩略表示。另外，当表述某个参数为≥2的整数，则相当于公开了该参数为例如整数2、3、4、5、6、7、8、9、10、11、12等。
如果没有特别的说明，本申请的所有实施方式以及可选实施方式可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有技术特征以及可选技术特征可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有步骤可以顺序进行，也可以随机进行，优选是顺序进行的。例如，所述方法包括步骤(a)和(b)，表示所述方法可包括顺序进行的步骤(a)和(b)，也可以包括顺序进行的步骤(b)和(a)。例如，所述提到所述方法还可包括步骤(c)，表示步骤(c)可以任意顺序加入到所述方法，例如，所述方法可以包括步骤(a)、(b)和(c)，也可包括步骤(a)、(c)和(b)，也可以包括步骤(c)、(a)和(b)等。
如果没有特别的说明，本申请所提到的“包括”和“包含”表示开放式，也可以是封闭式。例如，所述“包括”和“包含”可以表示 还可以包括或包含没有列出的其他组分，也可以仅包括或包含列出的组分。
如果没有特别的说明，在本申请中，术语“或”是包括性的。举例来说，短语“A或B”表示“A，B，或A和B两者”。更具体地，以下任一条件均满足条件“A或B”：A为真(或存在)并且B为假(或不存在)；A为假(或不存在)而B为真(或存在)；或A和B都为真(或存在)。
本申请的一个实施方式中，提供了用于锂离子二次电池的正极复合材料，其包含正极活性材料和式A mGO n所示的碱金属氧化物，其中，A代表选自Na和K中的至少一种元素和任选的Li，G代表选自Fe、Ni、Co、Mn、Ru、Ir、Sn、Cr、Nb、Mo、V和Ti中的至少一种元素，m为1～6，且n为1～4。其中，式A mGO n所示的碱金属氧化物，可以仅单独使用一种，也可以将两种以上组合使用。
本申请的发明人发现，在锂离子二次电池的使用过程中，随着正极活性材料中的锂离子在负极材料(例如石墨)中嵌入/脱出，负极材料不断发生膨胀/收缩，在充放电的过程中造成SEI膜不断破坏/修复，导致副产物不断增厚而引起膨胀。负极材料随锂离子的嵌入/脱出而不断膨胀/收缩会造成颗粒间粘结力降低，导致颗粒重排引起负极厚度增长，导致锂离子二次电池在使用过程中膨胀力不断增加。这种膨胀力的增加会导致电芯循环衰减加速和安全性能变差。
通过正极复合材料包含上述A mGO n所示的碱金属氧化物，利用离子半径较大的Na离子和/或K离子撑开负极材料，减小或消除因离子半径较小的锂离子在负极材料中反复嵌入/脱出而引起的负极材料的膨胀/收缩变形，减小或消除负极材料变形引起的SEI膜破坏，降低副反应，降低电芯膨胀力，改善电芯寿命并提升安全性能，从而有效地解决了上述问题。
在一些实施方式中，上述碱金属氧化物可以为选自Na 6FeO 4、K 6FeO 4、Na 6CoO 4、K 6CoO 4、Li 2Na 4FeO 4和Li 2K 4FeO 4中的至少一种。在正极复合材料中包含这些化合物时，能够利用Na离子和/或K离子可靠地撑开负极材料，从而获得上述技术效果。
在一些实施方式中，相对于总计100重量％的上述正极活性材料和 上述碱金属氧化物，上述碱金属氧化物的含量为0.1重量％～10重量％，优选为0.5重量％～4重量％。当碱金属氧化物比例低于0.1wt％时，Na、K等离子嵌入负极较少，无法很好地撑开负极材料，对循环和膨胀改善效果较小。当碱金属氧化物比例高于10wt％时，Na、K等离子大量嵌入负极，造成负极初始膨胀大，电芯内部留存较多空间来吸收膨胀，造成能量密度降低。
本申请的锂离子二次电池的正极包括上述的用于锂离子二次电池的正极复合材料。
另外，本申请不限定于上述碱金属氧化物与正极活性材料一起包含在正极复合材料中形成正极的构成，上述碱金属氧化物还可以作为独立的包含碱金属氧化物的碱金属氧化物层，与正极集流体、包含正极活性材料的正极活性材料层一起构成正极。
即，本申请还提供了一种锂离子二次电池的正极，其包括：正极集流体、包含正极活性材料的正极活性材料层、和包含碱金属氧化物的碱金属氧化物层，上述碱金属氧化物由式A mGO n表示，其中，A代表选自Na和K中的至少一种元素和任选的Li，G代表选自Fe、Ni、Co、Mn、Ru、Ir、Sn、Cr、Nb、Mo、V和Ti中的至少一种元素，m为1～6，且n为1～4。
通过具有这样的层结构，也能够利用离子半径较大的Na离子和/或K离子撑开负极材料，减小或消除因离子半径较小的锂离子在负极材料中反复嵌入/脱出而引起的负极材料的膨胀/收缩变形，减小或消除负极材料变形引起的SEI膜破坏，降低副反应，降低电芯膨胀力，从而改善电芯寿命并提升安全性能。
在一些实施方式中，上述碱金属氧化物可以为选自Na 6FeO 4、K 6FeO 4、Na 6CoO 4、K 6CoO 4、Li 2Na 4FeO 4和Li 2K 4FeO 4中的至少一种。在正极复合材料中包含这些化合物时，能够利用Na离子和/或K离子可靠地撑开负极材料，从而获得上述技术效果。
在一些实施方式中，上述碱金属氧化物层可以位于上述正极集流体与上述正极活性材料层之间、或者上述正极活性材料层之上。通过形成为这的层结构，能够更好地获得上述效果并且不会阻碍锂离子在正极与负极之间移动。
在一些实施方式中，相对于总计100重量％的上述正极活性材料层所含的正极活性材料和上述碱金属氧化物所含的碱金属氧化物，上述碱金属氧化物的含量为0.1重量％～10重量％，优选为0.5重量％～4重量％。当碱金属氧化物比例低于0.1wt％时，Na、K等离子嵌入负极较少，无法很好地撑开负极材料，对循环和膨胀改善效果较小。当碱金属氧化物比例高于10wt％时，Na、K等离子大量嵌入负极，造成负极初始膨胀大，电芯内部留存较多空间来吸收膨胀，造成能量密度降低。
本申请的锂离子二次电池包括含有上述正极复合材料的正极或具有上述层结构的正极、以及负极。
在一些实施方式中，上述负极包含负极活性材料，上述负极活性材料包含选自碳材料、金属或非金属的化合物以及上述化合物的包覆物和上述化合物的掺杂物中的至少一种。
在一些实施方式中，上述碳材料包含选自石墨、硬碳和软碳中的至少一种，上述金属或非金属的化合物包含选自硅、硒、硫、磷、锡、钛或钒的氧化物、硫化物、硒化物和氟化物中的至少一种，上述化合物的包覆物包含：用石墨、软碳或硬碳对上述金属或非金属的化合物进行包覆而得到的包覆物，上述化合物的掺杂物包含：用选自Mg、Ni、Co、Mn中的至少一种元素对上述金属或非金属的化合物进行掺杂而得到的掺杂物。在一些实施方式中，上述金属或非金属的化合物包含选自SiO 2、SiO、SnO 2、TiO 2、SiS 2和TiS 2中的至少一种。
通过使用这些物质作为锂离子二次电池的负极活性材料，能够更可靠地利用Na离子和/或K离子撑开负极材料，从而获得上述技术效果。
本申请的用电装置包括上述锂离子二次电池。
另外，以下适当参照附图对本申请的锂离子二次电池、电池模块、电池包和用电装置进行说明。
本申请的一个实施方式中，提供一种锂离子二次电池。
锂离子二次电池包括正极极片、负极极片、电解质和隔离膜。在电池充放电过程中，锂离子在正极极片和负极极片之间往返嵌入和脱出。电解质在正极极片和负极极片之间起到传导离子的作用。隔离膜 设置在正极极片和负极极片之间，主要起到防止正负极短路的作用，同时可以使离子通过。
[正极极片]
在一些实施方式中，正极极片包括正极集流体以及设置在正极集流体至少一个表面的正极复合材料层。
作为示例，正极集流体具有在其自身厚度方向相对的两个表面，正极复合材料层设置在正极集流体相对的两个表面的其中任意一者或两者上。
在一些实施方式中，上述正极集流体可采用金属箔片或复合集流体。例如，作为金属箔片，可采用铝箔。复合集流体可包括高分子材料基层和形成于高分子材料基层至少一个表面上的金属层。复合集流体可通过将金属材料(铝、铝合金、镍、镍合金、钛、钛合金、银及银合金等)形成在高分子材料基材(如聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)、聚乙烯(PE)等的基材)上而形成。
在一些实施方式中，正极复合材料层包含正极活性材料和式A mGO n所述的碱金属化合物，其中，A代表选自Na和K中的至少一种元素和任选的Li，G代表选自Fe、Ni、Co、Mn、Ru、Ir、Sn、Cr、Nb、Mo、V和Ti中的至少一种元素，m为1～6，且n为1～4。
在一些实施方式中，正极复合材料层中所包含的正极活性材料可采用本领域公知的用于电池的正极活性材料。
作为示例，正极活性材料可以为选自氧化物类正极材料或聚阴离子类正极材料中的至少一种。这些正极活性材料可以仅单独使用一种，也可以将两种以上组合使用。
作为上述氧化物类正极材料，可以列举LiNiO 2、LiCoO 2、LiMnO 2、LiNi xCo yMn zO 2(x+y+z＝1)或LiNi xCo yAl zO 2(x+y+z＝1)等层状氧化物、或者LiMn 2O 4等尖晶石型氧化物。
作为上述聚阴离子类正极材料，可以列举LiMPO 4(M为Fe、Co、Ni、Mn等)等橄榄石型正极材料、Li 2M 2(PO 4) 3(M为Fe、Co、Ni、Mn、Ti、V等)等具有NASICON型结构的正极材料、或者Li 2MSiO 4(M为Fe、Mn)等硅酸盐。
在一些实施方式中，正极复合材料层还可选地包括粘结剂。作为示例，上述粘结剂可以包括聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、偏氟乙烯-四氟乙烯-丙烯三元共聚物、偏氟乙烯-六氟丙烯-四氟乙烯三元共聚物、四氟乙烯-六氟丙烯共聚物及含氟丙烯酸酯树脂中的至少一种。
在一些实施方式中，正极复合材料层还可选地包括导电剂。作为示例，上述导电剂可以包括超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中的至少一种。
在一些实施方式中，例如可以通过以下方式制备正极极片：将例如正极活性材料和碱金属氧化物、导电剂、粘结剂和任意其他的组分分散于溶剂(例如N-甲基吡咯烷酮)中，形成正极浆料；将正极浆料涂覆在正极集流体上，经烘干、冷压等工序后，即可得到正极极片。
在另外的一些实施方式中，正极极片包括正极集流体、设置在正极集流体的至少一个表面的正极活性材料层、和位于正极集流体与正极活性材料层之间或正极活性材料层之上的碱金属氧化物层。上述碱金属氧化物式A mGO n所示的碱金属氧化物，其中，A代表选自Na和K中的至少一种元素和任选的Li，G代表选自Fe、Ni、Co、Mn、Ru、Ir、Sn、Cr、Nb、Mo、V和Ti中的至少一种元素，m为1～6，且n为1～4。
在这些实施方式中，正极集流体、碱金属氧化物、正极活性材料可以与上述实施方式相同，在此省略重复的说明。
在这些实施方式中，正极活性材料层和碱金属氧化物层还可选地包括粘结剂。作为示例，上述粘结剂可以包括聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、偏氟乙烯-四氟乙烯-丙烯三元共聚物、偏氟乙烯-六氟丙烯-四氟乙烯三元共聚物、四氟乙烯-六氟丙烯共聚物及含氟丙烯酸酯树脂中的至少一种。
在一些实施方式中，正极活性材料层和碱金属氧化物层还可选地包括导电剂。作为示例，上述导电剂可以包括超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中的至少一种。
在一些实施方式中，例如可以通过以下方式制备正极极片：将例如正极活性材料、导电剂、粘结剂和任意其他的组分分散于溶剂(例 如N-甲基吡咯烷酮)中，形成正极活性材料浆料；将正极活性材料浆料涂覆在正极集流体上，经烘干、冷压等工序得到正极活性材料层；将例如碱金属氧化物、导电剂、粘结剂和任意其他的组分分散于溶剂(例如N-甲基吡咯烷酮)中，形成碱金属氧化物浆料；再在所得到的正极活性材料层上涂覆碱金属氧化物浆料，经烘干、冷压等工序后，即可得到正极极片。在另外的实施方式中，可以将如上获得的碱金属氧化物浆料涂覆在正极集流体上，经烘干、冷压等工序得到碱金属氧化物层；再在所得到的碱金属氧化物层上涂覆如上获得的正极活性材料浆料，经烘干、冷压等工序后，得到正极极片。
[负极极片]
负极极片包括负极集流体以及设置在负极集流体至少一个表面上的负极材料层。
作为示例，负极集流体具有在其自身厚度方向相对的两个表面，负极材料层设置在负极集流体相对的两个表面中的任意一者或两者上。
在一些实施方式中，上述负极集流体可采用金属箔片或复合集流体。例如，作为金属箔片，可以采用铜箔。复合集流体可包括高分子材料基层和形成于高分子材料基材至少一个表面上的金属层。复合集流体可通过将金属材料(铜、铜合金、镍、镍合金、钛、钛合金、银及银合金等)形成在高分子材料基材(如聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)、聚乙烯(PE)等的基材)上而形成。
在一些实施方式中，负极材料层中可采用本领域公知的用于电池的负极活性材料。
作为示例，负极活性材料可包括以下材料中的至少一种：碳材料、金属或非金属的化合物以及上述化合物的包覆物和上述化合物的掺杂物等。上述碳材料包含选自石墨、硬碳和软碳中的至少一种，上述金属或非金属的化合物包含选自硅、硒、硫、磷、锡、钛或钒的氧化物、硫化物、硒化物和氟化物中的至少一种，上述化合物的包覆物包含：用石墨、软碳或硬碳对上述金属或非金属的化合物进行包覆而得到的包覆物，上述化合物的掺杂物包含：用选自Mg、Ni、Co、Mn中的至少一种元素对上述金属或非金属的化合物进行掺杂而得到的掺杂物。 在一些实施方式中，上述金属或非金属的化合物包含选自SiO 2、SiO、SnO 2、TiO 2、SiS 2和TiS 2中的至少一种。但本申请并不限定于这些材料，还可以使用其他可被用作电池负极活性材料的传统材料。这些负极活性材料可以仅单独使用一种，也可以将两种以上组合使用。
在一些实施方式中，负极材料层还可选地包括粘结剂。上述粘结剂可选自丁苯橡胶(SBR)、聚丙烯酸(PAA)、聚丙烯酸钠(PAAS)、聚丙烯酰胺(PAM)、聚乙烯醇(PVA)、海藻酸钠(SA)、聚甲基丙烯酸(PMAA)及羧甲基壳聚糖(CMCS)中的至少一种。
在一些实施方式中，负极材料层还可选地包括导电剂。导电剂可选自超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中的至少一种。
在一些实施方式中，负极材料层还可选地包括其他助剂，例如增稠剂(如羧甲基纤维素钠(CMC-Na))等。
在一些实施方式中，在制备负极材料层时还可以使用分散剂。分散剂用于提高分散均匀性和涂覆性，可以是电池领域中常用的分散剂，例如可以是聚合物分散剂。聚合物分散剂可以使用聚乙烯醇、具有羟基以外的官能团例如乙酰基、磺基、羧基、羰基、氨基的改性聚乙烯醇、通过各种盐改性、其他经阴离子或阳离子改性、通过醛类进行了缩醛改性的聚乙烯醇系树脂、或者各种(甲基)丙烯酸系聚合物、源于乙烯性不饱和烃的聚合物、各种纤维素系树脂等、或者这些的共聚物，但并不限定于这些。聚合物分散剂可单独使用一种，或者将两种以上组合使用。
在一些实施方式中，可以通过以下方式制备负极极片：将上述用于制备负极极片的组分，例如负极活性材料、导电剂、粘结剂和任意其他组分分散于溶剂(例如去离子水)中，形成负极浆料；将负极浆料涂覆在负极集流体上，经烘干、冷压等工序后，即可得到负极极片。
[电解质]
电解质在正极极片和负极极片之间起到传导离子的作用。本申请对电解质的种类没有具体的限制，可根据需求进行选择。例如，电解质可以是液态的、凝胶态的或全固态的。
在一些实施方式中，上述电解质采用电解液。上述电解液包括电 解质盐和溶剂。
在一些实施方式中，电解质盐可选自六氟磷酸锂、四氟硼酸锂、高氯酸锂、六氟砷酸锂、双氟磺酰亚胺锂、双三氟甲磺酰亚胺锂、三氟甲磺酸锂、二氟磷酸锂、二氟草酸硼酸锂、二草酸硼酸锂、二氟二草酸磷酸锂及四氟草酸磷酸锂中的至少一种。
在一些实施方式中，溶剂可选自碳酸亚乙酯、碳酸亚丙酯、碳酸甲乙酯、碳酸二乙酯、碳酸二甲酯、碳酸二丙酯、碳酸甲丙酯、碳酸乙丙酯、碳酸亚丁酯、氟代碳酸亚乙酯、甲酸甲酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丁酸甲酯、丁酸乙酯、1,4-丁内酯、环丁砜、二甲砜、甲乙砜及二乙砜中的至少一种。
在一些实施方式中，上述电解液还可选地包括添加剂。例如添加剂可以包括负极成膜添加剂、正极成膜添加剂，还可以包括能够改善电池某些性能的添加剂，例如改善电池过充性能的添加剂、改善电池高温或低温性能的添加剂等。
[隔离膜]
本申请中，锂离子二次电池中还包括隔离膜，本申请对隔离膜的种类没有特别的限制，可以选用任意公知的具有良好的化学稳定性和机械稳定性的多孔结构隔离膜。
在一些实施方式中，隔离膜的材质可选自玻璃纤维、无纺布、聚乙烯、聚丙烯及聚偏二氟乙烯中的至少一种。隔离膜可以是单层薄膜，也可以是多层复合薄膜，没有特别限制。在隔离膜为多层复合薄膜时，各层的材料可以相同或不同，没有特别限制。
[二次电池]
在一些实施方式中，正极极片、负极极片和隔膜可通过卷绕工艺或叠片工艺制成电极组件。
在一些实施方式中，锂离子二次电池可包括外包装。该外包装可用于封装上述电极组件及电解质。
在一些实施方式中，锂离子二次电池的外包装可以是硬壳，例如硬塑料壳、铝壳、钢壳等。锂离子二次电池的外包装也可以是软包，例如袋式软包。软包的材质可以是塑料，作为塑料，可列举出聚丙烯、聚对苯二甲酸丁二醇酯以及聚丁二酸丁二醇酯等。
本申请对锂离子二次电池的形状没有特别的限制，其可以是圆柱形、方形或其他任意的形状。例如，图1是作为一个示例的方形结构的锂离子二次电池5。
在一些实施方式中，参照图2，外包装可包括壳体51和盖板53。其中，壳体51可包括底板和连接于底板上的侧板，底板和侧板围合形成容纳腔。壳体51具有与容纳腔连通的开口，盖板53能够盖设于上述开口，以封闭上述容纳腔。正极极片、负极极片和隔离膜可经卷绕工艺或叠片工艺形成电极组件52。电极组件52封装于上述容纳腔内。电解液浸润于电极组件52中。锂离子二次电池5所含电极组件52的数量可以为一个或多个，本领域技术人员可根据具体实际需求进行选择。
在一些实施方式中，锂离子二次电池可以组装成电池模块，电池模块所含锂离子二次电池的数量可以为一个或多个，具体数量本领域技术人员可根据电池模块的应用和容量进行选择。
图3是作为一个示例的电池模块4。参照图3，在电池模块4中，多个二次电池5可以是沿电池模块4的长度方向依次排列设置。当然，也可以按照其他任意的方式进行排布。进一步可以通过紧固件将该多个二次电池5进行固定。
可选地，电池模块4还可以包括具有容纳空间的外壳，多个二次电池5容纳于该容纳空间。
在一些实施方式中，上述电池模块还可以组装成电池包，电池包所含电池模块的数量可以为一个或多个，具体数量本领域技术人员可根据电池包的应用和容量进行选择。
图4和图5是作为一个示例的电池包1。参照图4和图5，在电池包1中可以包括电池箱和设置于电池箱中的多个电池模块4。电池箱包括上箱体2和下箱体3，上箱体2能够盖设于下箱体3，并形成用于容纳电池模块4的封闭空间。多个电池模块4可以按照任意的方式排布于电池箱中。
另外，本申请还提供一种用电装置，上述用电装置包括本申请提供的锂离子二次电池。上述锂离子二次电池可以用作上述用电装置的电源，也可以用作上述用电装置的能量存储单元。上述用电装置可以 包括移动设备(例如手机、笔记本电脑等)、电动车辆(例如纯电动车、混合动力电动车、插电式混合动力电动车、电动自行车、电动踏板车、电动高尔夫球车、电动卡车等)、电气列车、船舶及卫星、储能系统等，但不限于此。
作为上述用电装置，可以根据其使用需求来选择锂离子二次电池、电池模块或电池包。
图6是作为一个示例的用电装置。该用电装置为纯电动车、混合动力电动车、或插电式混合动力电动车等。为了满足该用电装置对锂离子二次电池的高功率和高能量密度的需求，可以采用电池包或电池模块。
作为另一个示例的装置可以是手机、平板电脑、笔记本电脑等。该装置通常要求轻薄化，可以采用锂离子二次电池作为电源。
实施例
以下，说明本申请的实施例。下面描述的实施例是示例性的，仅用于解释本申请，而不能理解为对本申请的限制。实施例中未注明具体技术或条件的，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
实施例1：
二次电池的正极极片的制备：将正极活性材料LiNi 0.5Co 0.2Mn 0.3O 2、碱金属氧化物Na 6FeO 4、聚偏氟乙烯(PVDF)、导电剂(炭黑Super P)按质量比88:2:5:5混合，以N甲基-吡咯烷酮(NMP)为溶剂，调节溶剂的加入量，使浆料粘度控制在3000-20000mPa.s。使用涂布机将该浆料涂布在正极集流体上。在85℃下烘干后进行冷压，然后切边、裁片、分条，再在85℃真空条件下烘干4小时，焊接极耳，制成满足要求的二次电池正极极片。
二次电池的负极极片的制备：将负极活性材料石墨、导电剂Super-P、增稠剂CMC、粘接剂SBR按质量比96.5:1.0:1.0:1.5加入到溶剂去离子水中混合均匀制成负极浆料；将负极浆料涂布在集流体铜箔上并在85℃下烘干，然后进行切边、裁片、分条，再在110℃真空条件下烘干4小 时，焊接极耳，制成满足要求的二次电池负极极片。
二次电池的电解液的制备：以碳酸乙烯酯(EC)、碳酸丙烯酯(PC)以及碳酸二乙酯(DEC)的混合物为非水有机溶剂，其中各组分的质量比为EC:PC:DEC＝30:30:40，以六氟磷酸锂(LiPF 6)为锂盐，制成浓度为1M的电解液。
二次电池的制备：以12μm的聚丙烯薄膜作为隔离膜，将正极极片、隔离膜、负极极片按顺序叠好，使隔离膜处于正负极极片中间起到隔离的作用，然后卷绕成厚度为8mm、宽度为60mm、长度为130mm的方形裸电芯。将裸电芯装入铝箔包装袋，在75℃下真空烘烤10h，注入电解液、经过真空封装、静置24h，之后用0.1C(160mA)的恒定电流充电至4.5V，然后以4.5V恒压充电至电流下降到0.05C(80mA)，再以0.1C(160mA)的恒定电流放电至2.8V，重复2次充放电，最后以0.1C(160mA)的恒定电流充电至3.8V，即完成二次电池的制备。
实施例2：
二次电池的正极极片的制备：将正极活性材料LiNi 0.5Co 0.2Mn 0.3O 2、碱金属氧化物K 6FeO 4、聚偏氟乙烯(PVDF)、导电剂(炭黑Super P)按质量比89:1:5:5混合，以N甲基-吡咯烷酮(NMP)为溶剂，调节溶剂的加入量，使浆料粘度控制在3000-20000mPa.s。使用喷涂机将该浆料涂布在正极集流体上。在85℃下烘干后进行冷压，然后切边、裁片、分条，再在85℃真空条件下烘干4小时，焊接极耳，制成满足要求的二次电池正极极片。
二次电池的负极极片的制备：将负极活性材料石墨、导电剂Super-P、增稠剂CMC、粘接剂SBR按质量比96.5:1.0:1.0:1.5加入到溶剂去离子水中混合均匀制成负极浆料；将负极浆料涂布在集流体铜箔上并在85℃下烘干，然后进行切边、裁片、分条，再在110℃真空条件下烘干4小时，焊接极耳，制成满足要求的二次电池负极极片。
二次电池的电解液的制备：以碳酸乙烯酯(EC)、碳酸丙烯酯(PC)以及碳酸二乙酯(DEC)的混合物为非水有机溶剂，其中各组分的质量比为EC:PC:DEC＝30:30:40，以六氟磷酸锂(LiPF 6)为锂盐，制成浓度为1M的电解液。
二次电池的制备：以12μm的聚丙烯薄膜作为隔离膜，将正极极片、 隔离膜、负极极片按顺序叠好，使隔离膜处于正负极极片中间起到隔离的作用，然后卷绕成厚度为8mm、宽度为60mm、长度为130mm的方形裸电芯。将裸电芯装入铝箔包装袋，在75℃下真空烘烤10h，注入电解液、经过真空封装、静置24h，之后用0.1C(160mA)的恒定电流充电至4.5V，然后以4.5V恒压充电至电流下降到0.05C(80mA)，再以0.1C(160mA)的恒定电流放电至2.8V，重复2次充放电，最后以0.1C(160mA)的恒定电流充电至3.8V，即完成二次电池的制备。
实施例3：
二次电池的正极极片的制备：将正极活性材料LiNi 0.5Co 0.2Mn 0.3O 2、碱金属氧化物Li 2Na 4FeO 4、聚偏氟乙烯(PVDF)、导电剂(炭黑Super P)按质量比87.5:2.5:5:5混合，以N甲基-吡咯烷酮(NMP)为溶剂，调节溶剂的加入量，使浆料粘度控制在3000-20000mPa.s。使用涂布机将该浆料涂布在正极集流体上。在85℃下烘干后进行冷压，然后切边、裁片、分条，再在85℃真空条件下烘干4小时，焊接极耳，制成满足要求的二次电池正极极片。
二次电池的负极极片的制备：将负极活性材料石墨、导电剂Super-P、增稠剂CMC、粘接剂SBR按质量比96.5:1.0:1.0:1.5加入到溶剂去离子水中混合均匀制成负极浆料；将负极浆料涂布在集流体铜箔上并在85℃下烘干，然后进行切边、裁片、分条，再在110℃真空条件下烘干4小时，焊接极耳，制成满足要求的二次电池负极极片。
二次电池的电解液的制备：以碳酸乙烯酯(EC)、碳酸丙烯酯(PC)以及碳酸二乙酯(DEC)的混合物为非水有机溶剂，其中各组分的质量比为EC:PC:DEC＝30:30:40，以六氟磷酸锂(LiPF 6)为锂盐，制成浓度为1M的电解液。
二次电池的制备：以12μm的聚丙烯薄膜作为隔离膜，将正极极片、隔离膜、负极极片按顺序叠好，使隔离膜处于正负极极片中间起到隔离的作用，然后卷绕成厚度为8mm、宽度为60mm、长度为130mm的方形裸电芯。将裸电芯装入铝箔包装袋，在75℃下真空烘烤10h，注入电解液、经过真空封装、静置24h，之后用0.1C(160mA)的恒定电流充电至4.5V，然后以4.5V恒压充电至电流下降到0.05C(80mA)，再以0.1C(160mA)的恒定电流放电至2.8V，重复2次充放电，最后 以0.1C(160mA)的恒定电流充电至3.8V，即完成二次电池的制备。
实施例4：
二次电池的正极极片的制备：与实施例2同样操作，制成二次电池正极极片。
二次电池的负极极片的制备：在石墨中混合SiO得到混合物，其中SiO的量相对于上述混合物整体为25质量％，将所得到的混合物作为负极活性材料，将负极活性材料、导电剂Super-P、增稠剂CMC、粘接剂SBR按质量比96.5:1.0:1.0:1.5加入到溶剂去离子水中混合均匀制成负极浆料。除此之外，与实施例2同样操作，制成二次电池负极极片。
二次电池的电解液的制备：与实施例2同样操作，制成浓度为1M的电解液。
二次电池的制备：与实施例2同样操作，完成二次电池的制备。
实施例5：
二次电池的正极极片的制备：与实施例2同样操作，制成二次电池正极极片。
二次电池的负极极片的制备：在石墨中混合SiO碳包覆物得到混合物，其中SiO碳包覆物的量相对于上述混合物整体为25质量％，将该混合物作为负极活性材料，将负极活性材料、导电剂Super-P、增稠剂CMC、粘接剂SBR按质量比96.5:1.0:1.0:1.5加入到溶剂去离子水中混合均匀制成负极浆料。除此之外，与实施例2同样操作，制成二次电池负极极片。
二次电池的电解液的制备：与实施例2同样操作，制成浓度为1M的电解液。
二次电池的制备：与实施例2同样操作，完成二次电池的制备。
实施例6：
二次电池的正极极片的制备：与实施例2同样操作，制成二次电池正极极片。
二次电池的负极极片的制备：在石墨中混合用镁对SiO进行掺杂而得到的掺杂物(其中，镁相对于SiO镁掺杂物整体的量为0.1％～2％)，得到混合物，其中SiO镁掺杂物的量相对于上述混合物整体为25质 量％，将该混合物作为负极活性材料，将负极活性材料、导电剂Super-P、增稠剂CMC、粘接剂SBR按质量比96.5:1.0:1.0:1.5加入到溶剂去离子水中混合均匀制成负极浆料。除此之外，与实施例2同样操作，制成二次电池负极极片。
二次电池的电解液的制备：与实施例2同样操作，制成浓度为1M的电解液。
二次电池的制备：与实施例2同样操作，完成二次电池的制备。
实施例7：
二次电池的正极极片的制备：将正极活性材料LiNi 0.5Co 0.2Mn 0.3O 2、碱金属氧化物K 6FeO 4、聚偏氟乙烯(PVDF)、导电剂(炭黑Super P)按质量比89.91:0.09:5:5混合，除此之外，与实施例2同样操作，制成二次电池正极极片。
二次电池的负极极片的制备：与实施例2同样操作，制成满足二次电池负极极片。
二次电池的电解液的制备：与实施例2同样操作，制成浓度为1M的电解液。
二次电池的制备：与实施例2同样操作，完成二次电池的制备。
实施例8：
二次电池的正极极片的制备：将正极活性材料LiNi 0.5Co 0.2Mn 0.3O 2、碱金属氧化物K 6FeO 4、聚偏氟乙烯(PVDF)、导电剂(炭黑Super P)按质量比89.55:0.45:5:5混合，除此之外，与实施例2同样操作，制成二次电池正极极片。
二次电池的负极极片的制备：与实施例2同样操作，制成满足二次电池负极极片。
二次电池的电解液的制备：与实施例2同样操作，制成浓度为1M的电解液。
二次电池的制备：与实施例2同样操作，完成二次电池的制备。
实施例9：
二次电池的正极极片的制备：将正极活性材料LiNi 0.5Co 0.2Mn 0.3O 2、碱金属氧化物K 6FeO 4、聚偏氟乙烯(PVDF)、导电剂(炭黑Super P)按质量比86.4:3.6:5:5混合，除此之外，与实施例2同样操作，制成二 次电池正极极片。
二次电池的负极极片的制备：与实施例2同样操作，制成满足二次电池负极极片。
二次电池的电解液的制备：与实施例2同样操作，制成浓度为1M的电解液。
二次电池的制备：与实施例2同样操作，完成二次电池的制备。
实施例10：
二次电池的正极极片的制备：将正极活性材料LiNi 0.5Co 0.2Mn 0.3O 2、碱金属氧化物K 6FeO 4、聚偏氟乙烯(PVDF)、导电剂(炭黑Super P)按质量比81:9:5:5混合，除此之外，与实施例2同样操作，制成二次电池正极极片。
二次电池的负极极片的制备：与实施例2同样操作，制成满足二次电池负极极片。
二次电池的电解液的制备：与实施例2同样操作，制成浓度为1M的电解液。
二次电池的制备：与实施例2同样操作，完成二次电池的制备。
实施例11：
二次电池的正极极片的制备：将正极活性材料LiNi 0.5Co 0.2Mn 0.3O 2、碱金属氧化物K 6FeO 4、聚偏氟乙烯(PVDF)、导电剂(炭黑Super P)按质量比89.955:0.045:5:5混合，除此之外，与实施例2同样操作，制成二次电池正极极片。
二次电池的负极极片的制备：与实施例2同样操作，制成满足二次电池负极极片。
二次电池的电解液的制备：与实施例2同样操作，制成浓度为1M的电解液。
二次电池的制备：与实施例2同样操作，完成二次电池的制备。
实施例12：
二次电池的正极极片的制备：将正极活性材料LiNi 0.5Co 0.2Mn 0.3O 2、碱金属氧化物K 6FeO 4、聚偏氟乙烯(PVDF)、导电剂(炭黑Super P)按质量比80.1:9.9:5:5混合，除此之外，与实施例2同样操作，制成二次电池正极极片。
二次电池的负极极片的制备：与实施例2同样操作，制成满足二次电池负极极片。
二次电池的电解液的制备：与实施例2同样操作，制成浓度为1M的电解液。
二次电池的制备：与实施例2同样操作，完成二次电池的制备。
实施例13：
二次电池的正极极片的制备：将碱金属氧化物Na 6FeO 4与聚偏氟乙烯(PVDF)、导电剂(炭黑Super P)混合，以N甲基-吡咯烷酮(NMP)为溶剂，调节溶剂的加入量，使浆料粘度控制在3000-20000mPa.s。使用涂布机将该浆料涂布在正极集流体上，形成碱金属氧化物层。
再将正极活性材料LiNi 0.5Co 0.2Mn 0.3O 2与聚偏氟乙烯(PVDF)、导电剂(炭黑Super P)混合，使得LiNi 0.5Co 0.2Mn 0.3O 2与涂布在正极集流体上的碱金属氧化物Na 6FeO 4的质量比为88:2，N甲基-吡咯烷酮(NMP)为溶剂，调节溶剂的加入量，使浆料粘度控制在3000-20000mPa.s。使用涂布机将该浆料涂布在碱金属氧化物层上。
在85℃下烘干后进行冷压，然后切边、裁片、分条，再在85℃真空条件下烘干4小时，焊接极耳，制成二次电池正极极片。
二次电池的负极极片的制备：与实施例1同样操作，制成二次电池负极极片。
二次电池的电解液的制备：与实施例1同样操作，制成浓度为1M的电解液。
二次电池的制备：与实施例1同样操作，完成二次电池的制备。
实施例14：
二次电池的正极极片的制备：将正极活性材料LiNi 0.5Co 0.2Mn 0.3O 2与聚偏氟乙烯(PVDF)、导电剂(炭黑Super P)混合，N甲基-吡咯烷酮(NMP)为溶剂，调节溶剂的加入量，使浆料粘度控制在3000-20000mPa.s。使用涂布机将该浆料涂布在正极集流体上，形成正极活性材料层。
再将碱金属氧化物Na 6FeO 4与聚偏氟乙烯(PVDF)、导电剂(炭黑Super P)混合，使得碱金属氧化物Na 6FeO 4与涂布在正极集流体上的LiNi 0.5Co 0.2Mn 0.3O 2的质量比为2:88，以N甲基-吡咯烷酮(NMP) 为溶剂，调节溶剂的加入量，使浆料粘度控制在3000-20000mPa.s。使用涂布机将该浆料涂布在正极活性材料层上。
在85℃下烘干后进行冷压，然后切边、裁片、分条，再在85℃真空条件下烘干4小时，焊接极耳，制成二次电池正极极片。
二次电池的负极极片的制备：与实施例1同样操作，制成满足二次电池负极极片。
二次电池的电解液的制备：与实施例1同样操作，制成浓度为1M的电解液。
二次电池的制备：与实施例1同样操作，完成二次电池的制备。
实施例15：
二次电池的正极极片的制备：将正极活性材料LiNi 0.5Co 0.2Mn 0.3O 2、碱金属氧化物Na 6CoO 4、聚偏氟乙烯(PVDF)、导电剂(炭黑Super P)按质量比88:2:5:5混合，除此之外，与实施例1同样操作，制成二次电池正极极片。
二次电池的负极极片的制备：与实施例1同样操作，制成满足二次电池负极极片。
二次电池的电解液的制备：与实施例1同样操作，制成浓度为1M的电解液。
二次电池的制备：与实施例1同样操作，完成二次电池的制备。
对比例1：
二次电池的正极极片的制备：将正极活性材料LiNi 0.5Co 0.2Mn 0.3O 2、聚偏氟乙烯(PVDF)、导电剂(炭黑Super P)按质量比90:5:5混合，以N甲基-吡咯烷酮(NMP)为溶剂，调节溶剂的加入量，使浆料粘度控制在3000-20000mPa.s。使用涂布机将该浆料涂布在正极集流体上。在85℃下烘干后进行冷压，然后切边、裁片、分条，再在85℃真空条件下烘干4小时，焊接极耳，制成满足要求的二次电池正极极片。
二次电池的负极极片的制备：将负极活性材料石墨、导电剂Super-P、增稠剂CMC、粘接剂SBR按质量比96.5:1.0:1.0:1.5加入到溶剂去离子水中混合均匀制成负极浆料；将负极浆料涂布在集流体铜箔上并在85℃下烘干，然后进行切边、裁片、分条，再在110℃真空条件下烘干4小时，焊接极耳，制成满足要求的二次电池负极极片。
二次电池的电解液的制备：以碳酸乙烯酯(EC)、碳酸丙烯酯(PC)以及碳酸二乙酯(DEC)的混合物为非水有机溶剂，其中各组分的质量比为EC:PC:DEC＝30:30:40，以六氟磷酸锂(LiPF 6)为锂盐，制成浓度为1M的电解液。
二次电池的制备：以12μm的聚丙烯薄膜作为隔离膜，将正极极片、隔离膜、负极极片按顺序叠好，使隔离膜处于正负极极片中间起到隔离的作用，然后卷绕成厚度为8mm、宽度为60mm、长度为130mm的方形裸电芯。将裸电芯装入铝箔包装袋，在75℃下真空烘烤10h，注入电解液、经过真空封装、静置24h，之后用0.1C(160mA)的恒定电流充电至4.5V，然后以4.5V恒压充电至电流下降到0.05C(80mA)，再以0.1C(160mA)的恒定电流放电至2.8V，重复2次充放电，最后以0.1C(160mA)的恒定电流充电至3.8V，即完成二次电池的制备。
对比例2：
二次电池的正极极片的制备：将正极活性材料LiNi 0.5Co 0.2Mn 0.3O 2、聚偏氟乙烯(PVDF)、导电剂(炭黑Super P)按质量比90:5:5混合，以N甲基-吡咯烷酮(NMP)为溶剂，调节溶剂的加入量，使浆料粘度控制在3000-20000mPa.s。使用涂布机将该浆料涂布在正极集流体上。在85℃下烘干后进行冷压，然后切边、裁片、分条，再在85℃真空条件下烘干4小时，焊接极耳，制成满足要求的二次电池正极极片。
二次电池的负极极片的制备：在石墨中混合SiO得到混合物，其中SiO的量相对于上述混合物整体为25质量％，将所得到的混合物作为负极活性材料，将负极活性材料、导电剂Super-P、增稠剂CMC、粘接剂SBR按质量比96.5:1.0:1.0:1.5加入到溶剂去离子水中混合均匀制成负极浆料。除此之外，与实施例2同样操作，制成二次电池负极极片。
二次电池的电解液的制备：以碳酸乙烯酯(EC)、碳酸丙烯酯(PC)以及碳酸二乙酯(DEC)的混合物为非水有机溶剂，其中各组分的质量比为EC:PC:DEC＝30:30:40，以六氟磷酸锂(LiPF 6)为锂盐，制成浓度为1M的电解液。
二次电池的制备：以12μm的聚丙烯薄膜作为隔离膜，将正极极片、隔离膜、负极极片按顺序叠好，使隔离膜处于正负极极片中间起到隔 离的作用，然后卷绕成厚度为8mm、宽度为60mm、长度为130mm的方形裸电芯。将裸电芯装入铝箔包装袋，在75℃下真空烘烤10h，注入电解液、经过真空封装、静置24h，之后用0.1C(160mA)的恒定电流充电至4.5V，然后以4.5V恒压充电至电流下降到0.05C(80mA)，再以0.1C(160mA)的恒定电流放电至2.8V，重复2次充放电，最后以0.1C(160mA)的恒定电流充电至3.8V，即完成二次电池的制备。
将上述实施例1～15、对比例1～2的二次电池的正极和负极的构成示于以下表1。
[表1]
Figure PCTCN2022072029-appb-000001
循环性能、膨胀力和能量密度的测试
在45℃下，对上述实施例1～15、对比例1～2的二次电池进行1C/1C循环测试，充放电电压范围为2.8～4.5V，容量衰减至首次放电比容量的80％时停止测试，记录循环次数和膨胀力。
在2.8V-4.3V电压范围内，以1C电流测试电芯能量，除以电芯重量即可得到能量密度。
上述实施例1～15、对比例1～2的二次电池的相关参数如下述表2所示。
[表2]
分类 循环寿命(次) EOL电芯膨胀力(N) 能量密度(Wh/kg)
实施例1 2500 10000 244
实施例2 2400 7000 244.5
实施例3 2700 8000 243.8
实施例4 2000 20000 259
实施例5 2200 18000 259
实施例6 2300 17000 259
实施例7 2100 9000 245
实施例8 2200 8000 245
实施例9 2700 6500 258
实施例10 2600 6000 254
实施例11 1800 11000 245
实施例12 1500 10000 250
实施例13 2500 10000 244
实施例14 2500 10000 244
实施例15 2500 10000 253
对比例1 1200 30000 245
对比例2 800 60000 260
根据上述结果可知，在实施例1～15中，用于形成正极的正极复合材料中包含碱金属氧化物，或者正极包括由碱金属氧化物形成的碱金属氧化物层，获得了电芯膨胀力低、循环寿命高、能量密度优异的技术效果。
而相对于此，对比例1、2中，由于正极中不含碱金属氧化物，电芯膨胀力明显高于实施例，循环寿命也差。
需要说明的是，本申请不限定于上述实施方式。上述实施方式仅为示例，在本申请的技术方案范围内具有与技术思想实质相同的构成、发挥相同作用效果的实施方式均包含在本申请的技术范围内。此外，在不脱离本申请主旨的范围内，对实施方式施加本领域技术人员能够想到的各种变形、将实施方式中的一部分构成要素加以组合而构筑的其它方式也包含在本申请的范围内。

Claims (13)

  1. 一种用于锂离子二次电池的正极复合材料，其特征在于，
    包含正极活性材料和式A mGO n所示的碱金属氧化物，其中，A代表选自Na和K中的至少一种元素和任选的Li，G代表选自Fe、Ni、Co、Mn、Ru、Ir、Sn、Cr、Nb、Mo、V和Ti中的至少一种元素，m为1～6，且n为1～4。
  2. 根据权利要求1所述的正极复合材料，其特征在于，
    所述碱金属氧化物为选自Na 6FeO 4、K 6FeO 4、Na 6CoO 4、K 6CoO 4、Li 2Na 4FeO 4和Li 2K 4FeO 4中的至少一种。
  3. 根据权利要求1或2所述的正极复合材料，其特征在于，
    相对于总计100重量％的所述正极活性材料和所述碱金属氧化物，所述碱金属氧化物的含量为0.1重量％～10重量％，优选为0.5重量％～4重量％。
  4. 一种锂离子二次电池的正极，其特征在于，
    包括根据权利要求1～3中任一项所述的正极复合材料。
  5. 一种锂离子二次电池的正极，其特征在于，包括：
    正极集流体、包含正极活性材料的正极活性材料层、和包含碱金属氧化物的碱金属氧化物层，
    所述碱金属氧化物由式A mGO n表示，其中，A代表选自Na和K中的至少一种元素和任选的Li，G代表选自Fe、Ni、Co、Mn、Ru、Ir、Sn、Cr、Nb、Mo、V和Ti中的至少一种元素，m为1～6，且n为1～4。
  6. 根据权利要求5所述的锂离子二次电池的正极，其特征在于，
    所述碱金属氧化物为选自Na 6FeO 4、K 6FeO 4、Na 6CoO 4、K 6CoO 4、Li 2Na 4FeO 4和Li 2K 4FeO 4中的至少一种。
  7. 根据权利要求5或6所述的锂离子二次电池的正极，其特征在于，
    所述碱金属氧化物层位于所述正极集流体与所述正极活性材料层之间、或者所述正极活性材料层之上。
  8. 根据权利要求5～7中任一项所述的锂离子二次电池的正极，其特征在于，
    相对于总计100重量％的所述正极活性材料和所述碱金属氧化物，所述碱金属氧化物的含量为0.1重量％～10重量％，优选为0.5重量％～4重量％。
  9. 一种锂离子二次电池，其特征在于，
    包括根据权利要求4～8中任一项所述的锂离子二次电池的正极和负极。
  10. 根据权利要求9所述的锂离子二次电池，其特征在于，
    所述负极包含负极活性材料，
    所述负极活性材料包含选自碳材料、金属或非金属的化合物以及所述化合物的包覆物和所述化合物的掺杂物中的至少一种。
  11. 根据权利要求10所述的锂离子二次电池，其特征在于，
    所述碳材料包含选自石墨、硬碳和软碳中的至少一种，
    所述金属或非金属的化合物包含选自硅、硒、硫、磷、锡、钛或钒的氧化物、硫化物、硒化物和氟化物中的至少一种，
    所述化合物的包覆物包含：用石墨、软碳或硬碳对所述金属或非金属的化合物进行包覆而得到的包覆物，
    所述化合物的掺杂物包含：用选自Mg、Ni、Co、Mn中的至少一种元素对所述金属或非金属的化合物进行掺杂而得到的掺杂物。
  12. 根据权利要求10或11所述的锂离子二次电池，其特征在于，
    所述金属或非金属的化合物包含选自SiO 2、SiO、SnO 2、TiO 2、SiS 2 和TiS 2中的至少一种。
  13. 一种用电装置，其特征在于，
    包括根据权利要求9～12中任一项所述的锂离子二次电池。
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