WO2018137169A1 - 锂离子电池及其制备方法 - Google Patents

锂离子电池及其制备方法 Download PDF

Info

Publication number
WO2018137169A1
WO2018137169A1 PCT/CN2017/072568 CN2017072568W WO2018137169A1 WO 2018137169 A1 WO2018137169 A1 WO 2018137169A1 CN 2017072568 W CN2017072568 W CN 2017072568W WO 2018137169 A1 WO2018137169 A1 WO 2018137169A1
Authority
WO
WIPO (PCT)
Prior art keywords
lithium
positive electrode
ion battery
lithium ion
electrolyte
Prior art date
Application number
PCT/CN2017/072568
Other languages
English (en)
French (fr)
Chinese (zh)
Inventor
张晶晶
Original Assignee
罗伯特·博世有限公司
张晶晶
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 罗伯特·博世有限公司, 张晶晶 filed Critical 罗伯特·博世有限公司
Priority to PCT/CN2017/072568 priority Critical patent/WO2018137169A1/zh
Priority to CN201780075404.9A priority patent/CN110036523A/zh
Priority to KR1020197021700A priority patent/KR20190103232A/ko
Priority to DE112017006921.1T priority patent/DE112017006921T5/de
Publication of WO2018137169A1 publication Critical patent/WO2018137169A1/zh

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • H01M10/058—Construction or manufacture
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/044—Activating, forming or electrochemical attack of the supporting material
    • H01M4/0445—Forming after manufacture of the electrode, e.g. first charge, cycling
    • H01M4/0447—Forming after manufacture of the electrode, e.g. first charge, cycling of complete cells or cells stacks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/0459—Electrochemical doping, intercalation, occlusion or alloying
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present disclosure provides a novel lithium ion battery comprising a positive electrode, a negative electrode and an electrolyte, wherein the positive electrode comprises a positive active material and a pre-lithiation lithium source selected from the group consisting of LiVO 3 , LiV 3 O 8. Li 3 VO 4 , Li 2 C 2 and any combination thereof, preferably Li 2 C 2 .
  • the invention also provides a preparation method of the lithium ion battery.
  • lithium ion batteries have been widely used in energy storage systems and electronic devices.
  • lithium ions migrate from the positive electrode to the negative electrode during charging.
  • a lithium-containing positive electrode material for example, LiCoO 2 or LiNiO 2
  • a negative electrode material for example, graphite
  • an electrolytic solution lithium ions migrate from the positive electrode to the negative electrode during charging.
  • lithium ions inevitably continue to react with the electrolyte, thereby undesirably consuming lithium and forming a solid electrolyte interface (SEI) on the anode.
  • SEI solid electrolyte interface
  • the consumed lithium does not return to the positive electrode, causing rapid decay of the capacity of the lithium ion battery.
  • the inventors of the present invention have developed a novel lithium ion battery comprising a positive electrode, a negative electrode and an electrolyte, wherein the positive electrode comprises a positive electrode active material and a lithium pre-lithiation source selected from the group consisting of LiVO 3 , LiV 3 O 8 , Li 3 VO 4 , Li 2 C 2 and any combination thereof, preferably Li 2 C 2 .
  • the present disclosure also provides a method of preparing the lithium ion battery, the method comprising the steps of:
  • a positive electrode comprising a positive active material and a lithium pre-lithiation source selected from the group consisting of LiVO 3 , LiV 3 O 8 , Li 3 VO 4 , Li 2 C 2 and any combination thereof, preferably Li 2 C 2 ;
  • the present disclosure also provides a lithium ion battery comprising a positive electrode, a negative electrode and an electrolyte, wherein the electrolyte comprises a lithium salt, a non-aqueous solvent, and a pre-lithiation lithium source selected from the group consisting of LiVO 3 , LiV 3 O 8 Li 3 VO 4 , Li 2 C 2 and any combination thereof, preferably Li 2 C 2 ;
  • the electrolyte further comprises a boron based anion acceptor.
  • the present disclosure also provides a method of preparing the lithium ion battery, the method comprising the steps of:
  • the electrolyte comprising a lithium salt, a non-aqueous solvent and a pre-selected lithiated lithium source: LiVO 3, LiV 3 O 8 , Li 3 VO 4, Li 2 C 2 , and any combination thereof , preferably Li 2 C 2 ;
  • LiVO 3 , LiV 3 O 8 , Li 3 VO 4 and/or Li 2 C 2 , especially Li 2 C 2 can be advantageously used in the positive electrode and/or electrolysis of lithium ion batteries.
  • it serves as a lithium source for the pre-lithiated negative electrode.
  • Pre-lithiation of the negative electrode of a lithium ion battery by employing a particular pre-lithiation lithium source of the present invention can compensate for capacity degradation and significantly improve battery performance (e.g., irreversible capacity and cycle stability).
  • lithium powder Since lithium powder has high activity against moisture in the air, hydrogen gas is released during the reaction, and therefore, there is a risk of explosion when lithium powder is used in the battery.
  • the particular pre-lithiation lithium source employed in the present invention is relatively stable to moisture in the air.
  • Li 2 C 2 when Li 2 C 2 is used as the lithium source of pre-lithiation, even if Li 2 C 2 reacts with moisture, it is considered that Li 2 C 2 is composed only of elemental lithium and carbon, and the reaction product does not contain undesired The impurities are less likely to cause side reactions due to the introduced impurities, thereby impairing battery performance. Moreover, if Li 2 C 2 reacts with moisture in the air and does not blast due to gas generation, the preparation of the battery does not require a harsh vacuum environment, which greatly improves production safety and reduces production costs.
  • a specific pre-lithiation lithium source can be supplied to the positive electrode or the electrolyte. Since the specific pre-lithiation lithium source used in the present invention is compatible with the positive electrode or other components contained in the electrolyte, it is not necessary to change the composition of the positive electrode or the electrolyte. However, if the lithium powder is directly supplied to the negative electrode, it is necessary to adjust the solvent and the binder contained in the negative electrode accordingly.
  • Figure 1 is a schematic comparison of the charge/discharge performance of a comparative example with a battery prepared in accordance with an embodiment of the present invention.
  • Figure 2 is a schematic comparison of the cycling performance of a comparative example with a battery prepared in accordance with an embodiment of the present invention.
  • Ranges of values recited herein are intended to include the endpoints of the ranges, and all values and all sub-ranges within the range.
  • lithium ion battery is used interchangeably with the term “battery.”
  • the term “comprising” or “including” as used herein means that other components or other steps that do not affect the final effect may also be included or included.
  • the term “comprising” or “including” encompasses the "consisting of” and “consisting primarily of”.
  • the methods and products of the present disclosure may comprise or include the necessary technical features and/or defined features described herein to And any other and/or optionally present ingredients, components, steps or defined features described herein.
  • the methods and products of the present disclosure may also be constructed from the essential technical features and/or defined features described herein, or consist essentially of the essential technical features and/or defined features described herein.
  • positive electrode composition or "negative electrode composition” means a composition for forming a positive electrode slurry or a negative electrode slurry.
  • the positive electrode slurry or the negative electrode slurry may then be applied to a corresponding current collector, and after drying, a positive electrode or a negative electrode may be formed.
  • a lithium ion battery comprising a positive electrode, a negative electrode, and an electrolyte, wherein the positive electrode comprises a positive active material and a pre-lithiation lithium source selected from the group consisting of LiVO 3 , LiV 3 O 8 , Li 3 VO 4 , Li 2 C 2 and any combination thereof, preferably Li 2 C 2 .
  • a lithium ion battery comprising a positive electrode, a negative electrode, and an electrolyte, wherein the electrolyte comprises a lithium salt, a non-aqueous solvent, and a pre-lithiation lithium source selected from the group consisting of LiVO 3 , LiV 3 O 8 , Li 3 VO 4 , Li 2 C 2 and any combination thereof, preferably Li 2 C 2 ;
  • the electrolyte further comprises a boron based anion acceptor.
  • the lithium ion battery is pre-lithiated or not pre-lithiated.
  • the Li 2 C 2 content is from greater than 0 to about 20% by weight, preferably from greater than 0 to less than 20% by weight, more preferably from about 0.01% to about 5% by weight, based on the total dry weight of the positive electrode composition, Still more preferably from about 0.01% by weight to about 1% by weight.
  • a method of making a lithium ion battery in accordance with the present disclosure comprising the steps of:
  • a positive electrode comprising a positive active material and a lithium pre-lithiation source selected from the group consisting of LiVO 3 , LiV 3 O 8 , Li 3 VO 4 , Li 2 C 2 and any combination thereof, preferably Li 2 C 2 ;
  • a method of making a lithium ion battery in accordance with the present disclosure comprising the steps of:
  • an electrolyte comprising a lithium salt, a non-aqueous solvent, and a pre-lithiation lithium source selected from the group consisting of LiVO 3 , LiV 3 O 8 , Li 3 VO 4 , Li 2 C 2 , and any combination thereof , preferably Li 2 C 2 ;
  • the content of Li 2 C 2 in the pre-lithiated or unpre-lithiated cell is greater than 0 to about 20% by weight, preferably greater than 0 to less than 20, based on the total dry weight of the positive electrode composition. % by weight, more preferably from about 0.01% to about 5% by weight, still more preferably from about 0.01% to about 1% by weight.
  • the inventors of the present invention have surprisingly found that by providing the lithium ion battery of the present disclosure, on the one hand, the SEI can be stabilized, the capacity attenuation can be compensated, and the battery performance (e.g., irreversible capacity and cycle stability) can be significantly improved. On the other hand, undesired lithium dendrites can be avoided.
  • the particular pre-lithiation lithium source employed in the present invention is relatively stable to moisture in the air.
  • Li 2 C 2 when Li 2 C 2 is used as the lithium source of pre-lithiation, even if Li 2 C 2 reacts with moisture, it is considered that Li 2 C 2 is composed only of elemental lithium and carbon, and the reaction product does not contain undesired
  • the impurities are less likely to cause side reactions due to the introduced impurities, thereby impairing battery performance.
  • Li 2 C 2 reacts with moisture in the air and does not blast due to gas generation, the preparation of the battery does not require a harsh vacuum environment, which greatly improves production safety and reduces production costs.
  • a specific pre-lithiation lithium source can be supplied to the positive electrode or the electrolyte. Since the specific pre-lithiation lithium source used in the present invention is compatible with the positive electrode or other components contained in the electrolyte, it is not necessary to change the composition of the positive electrode or the electrolyte. However, if lithium is to be When the powder is directly supplied to the negative electrode, it is necessary to adjust the solvent and the binder contained in the negative electrode accordingly.
  • a positive electrode including a positive electrode active material and a pre-lithiation lithium source (particularly Li 2 C 2 )
  • a positive electrode active material and a pre-lithium lithium source may be used to form a positive electrode slurry, and then the positive electrode slurry is used.
  • a pre-lithiation lithium source (particularly Li 2 C 2 ) may be mixed with other components of the positive electrode composition to form a positive electrode slurry, wherein other components of the positive electrode composition include, for example, a positive active material, a carbon material , binders, solvents and/or additives optionally present.
  • the positive electrode slurry can be applied to the positive electrode current collector by, for example, coating, thereby forming a positive electrode including a pre-lithiation lithium source.
  • a pre-lithiation lithium source can be easily introduced into the positive electrode.
  • the introduction step of the pre-lithium lithiation source is integrated with the addition step of the other components of the positive electrode (integrated), no additional separate addition steps are required, and no special operating conditions are required, which means considerable cost for industrial production. Reduced and labor saved.
  • a positive electrode including a positive electrode active material and a pre-lithiation lithium source (particularly Li 2 C 2 )
  • a positive electrode active material may also be applied to the positive electrode current collector to form an active material layer, and then the pre-lithium may be used.
  • a lithium source (particularly Li 2 C 2 ) is applied to the active material layer to form a pre-lithiated lithium source layer. Providing a pre-lithiation lithium source in this manner is also easy to implement.
  • a lithium ion battery according to the present disclosure can be used in an energy storage system and an electronic device.
  • lithium ions are released from a particular pre-lithiation lithium source of the positive or electrolyte during the first few (eg, 1-5) charging cycles.
  • the released lithium ions are inserted into the negative electrode and stored in the negative electrode, thereby pre-lithiation of the negative electrode. Therefore, the first several charging processes of pre-lithiation of the negative electrode are also referred to as "formation” or “formation charge”.
  • lithium stored in the negative electrode during the formation process can participate in lithium ion migration, compensate for lithium lost due to formation of the SEI layer, stabilize the SEI layer, and reduce capacity degradation.
  • the negative electrode may be partially pre-lithiated to compensate for lithium lost due to formation of SEI and to retain the desired lithium migration between the positive and negative electrodes.
  • the formation may be performed over a range of voltages, also referred to as the "cutoff voltage" range.
  • the upper limit of the cutoff voltage is no less than about 3.8V but no greater than about 5V, preferably no less than about 4.2V but no greater than about 5V.
  • the upper limit of the cutoff voltage depends on the positive active material contained in the lithium ion battery.
  • the positive electrode active material will be described in detail below.
  • the upper limit of the cutoff voltage during the formation is not lower than about 4.2 V but not higher than about 5 V.
  • the upper limit of the cutoff voltage during the formation process is not less than about 4.35 V but not Above about 5V.
  • the lithium ion source can sufficiently release lithium ions, and on the other hand, the positive electrode is not seriously damaged.
  • the irreversible capacity (unit: mAh/cm 2 ) of the negative electrode usable for intercalating lithium is irreversible of the positive electrode
  • the capacity (unit: mAh/cm 2 ) is from about 1 time to about 1.4 times, preferably from about 1 time to about 1.2 times, more preferably from about 1 time to about 1.1 times.
  • the ratio of the irreversible capacity of the negative electrode to the irreversible capacity of the positive electrode is one. However, considering that there is inevitably an operational error in the process of preparing the battery, the ratio may be greater than one. If the ratio of the irreversible capacity of the negative electrode to the irreversible capacity of the positive electrode is from 1 to about 1.4, it is possible to avoid formation of lithium dendrites around the negative electrode without excessively consuming the irreversible capacity of the negative electrode.
  • the lithium ion battery can be pre-lithiated or not pre-lithiated.
  • the positive electrode composition may comprise a pre-lithiation lithium source selected from the group consisting of LiVO 3 , LiV 3 O 8 , Li 3 VO 4 , Li 2 C 2 , and any combination thereof.
  • the pre-lithiation lithium source is used to pre-lithiation the negative electrode.
  • the Li 2 C 2 content is from greater than 0 to about 20% by weight, preferably from greater than 0 to less than 20% by weight, more preferably from about 0.01% to about 5% by weight, based on the total dry weight of the positive electrode composition, Still more preferably from about 0.01% by weight to about 1% by weight. If the content of the pre-lithiation lithium source falls within the above range, on the one hand, lithium which is lost due to the formation of SEI can be sufficiently compensated, and on the other hand, undesired lithium dendrites can be avoided.
  • the positive electrode composition may contain traces of a source of pre-lithiation lithium.
  • the content of Li 2 C 2 is from about 0.01% to about 1 wt%.
  • Li 2 C 2 can be produced by a known method using lithium and carbon as raw materials.
  • Jiangtao He et al. "Preparation and phase stability of nanocrystalline Li 2 C 2 alloy", Materials Letters 94 (2013), pages 176-178, discloses a process for preparing Li 2 C 2 . This document is incorporated herein by reference in its entirety.
  • the particle size of the pre-lithiation lithium source is not particularly limited, and nanometer-sized (less than 1 micrometer) or micrometer-sized (greater than 1 micrometer but less than 1 millimeter) particle size can be used in the present disclosure; nanoscale is preferred.
  • the positive electrode in addition to the pre-lithiation lithium source, may further comprise a lithium-based active material.
  • the positive active material is a material that can reversibly deintercalate and intercalate lithium ions in a charge/discharge cycle. In the discharge cycle, lithium ions obtained from the positive electrode active material can be returned from the negative electrode to the positive electrode to form the positive electrode active material again.
  • the prelithium lithium source may be referred to as an "extra lithium source” or an “additional lithium source” relative to the positive active material used as the base lithium source.
  • the positive electrode active material is not particularly limited, and a positive electrode active material which is commonly used in a lithium ion battery can be used in the present disclosure.
  • the positive active material may be different from the pre-lithiation lithium source.
  • the positive active material may be selected from the group consisting of lithium-metal oxides, lithium-metal phosphates, lithium-metal silicates, sulfides, and any combination thereof, preferably lithium-transition metal composite oxides, lithium-transitions Metal phosphates, lithium-metal silicates, metal sulfides, and any combination thereof.
  • the lithium-transition metal phosphate can be selected from the group consisting of lithium iron phosphate, lithium manganese phosphate, lithium manganese phosphate, and any combination thereof.
  • the lithium-transition metal composite oxide may be selected from the group consisting of lithium nickel oxide, lithium cobalt oxide, lithium manganese oxide, lithium nickel cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide (NCM).
  • NCM lithium nickel cobalt aluminum oxide
  • the metal sulfide can be iron sulfide.
  • the positive electrode composition may further contain a carbon material in addition to the pre-lithiation lithium source and the positive electrode active material.
  • Carbon material refers to a material containing carbon.
  • a carbon material can be used to improve the conductivity and/or the fraction of the battery positive electrode composition. Scattered.
  • the carbon material is not particularly limited, and a carbon material commonly used for a lithium ion battery can be used in the present disclosure.
  • the carbon material may be selected from the group consisting of carbon black, superconducting carbon black (eg, Super P from Timcal Corporation), acetylene black, ketjen black, graphite, graphene, carbon nanotubes, carbon fiber, vapor grown Carbon fiber and combinations thereof.
  • a mixture of two or more carbon materials may be included in the positive electrode composition.
  • the positive electrode composition may simultaneously contain two or more carbon materials having different particle diameters, for example, a carbon material having a particle diameter of not less than 1 ⁇ m, and the same or different kinds of carbon having a particle diameter of less than 1 ⁇ m. material.
  • the positive electrode composition may further include a binder in addition to the pre-lithiation lithium source and the positive electrode active material.
  • the binder may bond the components of the cathode composition together and adhere the cathode composition to the cathode current collector.
  • the binder helps the positive electrode maintain good stability and integrity when repeated charge/discharge cycles cause volume changes, thereby improving the electrochemical performance (including cycling performance and rate performance) of the final cell.
  • the binder can be polyvinylidene fluoride (PVDF), polyacrylic acid (PAA), sodium carboxymethylcellulose (CMC), preferably PVDF.
  • the positive electrode composition may further comprise a solvent.
  • the solvent can be used to dissolve other components in the positive electrode composition to provide a positive electrode slurry. Then, the obtained positive electrode slurry can be applied to the positive electrode current collector and dried to obtain a positive electrode.
  • the solvent contained in the positive electrode composition is not particularly limited, and a solvent commonly used in a lithium ion battery can be used in the present disclosure.
  • the solvent in the positive electrode composition may be N-methyl-2-pyrrolidone (NMP).
  • the positive electrode composition may include a pre-lithiation lithium source, a positive electrode active material, a carbon material, a binder, and a solvent, wherein the pre-lithium lithiate is selected from the group consisting of LiVO 3 , LiV 3 O 8 , and Li 3 VO 4 . Li 2 C 2 and any combination thereof. Further, the positive electrode composition may also optionally contain other additives commonly used in lithium ion batteries as long as these additives do not adversely impair the desired properties of the battery.
  • cathode current collector there is no particular limitation on the cathode current collector.
  • aluminum foil can be used as Positive current collector.
  • the anode composition may include a cathode active material.
  • the negative electrode active material is not particularly limited, and a negative electrode active material which is commonly used in a lithium ion battery can be used in the present disclosure.
  • the negative active material may be selected from the group consisting of silicon-based active materials, carbon-based active materials, and any combination thereof.
  • Silicon-based active material refers to an active material containing silicon. Suitable silicon-based active materials can include, but are not limited to, silicon, silicon alloys, silicon oxides, silicon/carbon composites, and silicon oxide/carbon composites, and any combination thereof.
  • the silicon alloy may comprise silicon and one or more metals selected from the group consisting of titanium, tin, aluminum, lanthanum, cerium, arsenic, antimony, and lead.
  • the silicon oxide can be a mixture of two or more oxides of silicon, for example, the silicon oxide can be represented by SiO x with an average value of x of from about 0.5 to about 2.
  • the carbon-based active material in the negative electrode may be the same as or different from the carbon material contained in the positive electrode.
  • suitable carbon-based active materials may include, but are not limited to, graphite, graphene, hard carbon, carbon black, and carbon nanotubes.
  • the negative electrode composition may further contain a carbon material, a binder, and/or a solvent.
  • the carbon material, binder, and/or solvent in the negative electrode may be the same as or different from the carbon material, binder, and/or solvent contained in the positive electrode, respectively.
  • the negative electrode composition may also optionally contain other additives commonly used in lithium ion batteries as long as these additives do not adversely impair the desired properties of the battery.
  • anode current collector there is no particular limitation on the anode current collector.
  • a nickel foil, a nickel mesh, a copper foil, or a copper mesh can be used as the negative current collector.
  • a lithium ion battery may contain an electrolyte.
  • the electrolyte may comprise a lithium salt and a non-aqueous solvent.
  • the nonaqueous solvent may be different from or not containing water, and may be an inorganic solvent or an organic solvent.
  • the lithium salt and the nonaqueous solvent are not particularly limited, and those lithium salts and nonaqueous solvents known to be usable for lithium ion batteries can be used in the present disclosure.
  • the lithium salt in the electrolyte can be different from the positive active material and the pre-lithiation lithium source.
  • the lithium salt may include, but is not limited to, lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium arsenate (LiAsO 4 ), LiSbO 4 , lithium perchlorate (LiClO 4 ), LiAlO 4 .
  • LiPF 6 lithium hexafluorophosphate
  • LiBF 4 lithium tetrafluoroborate
  • LiAsO 4 lithium arsenate
  • LiSbO 4 Li perchlorate
  • LiClO 4 LiAlO 4
  • LiGaO 4 lithium bis(oxalate)borate
  • LiBOB lithium bis(oxalate)borate
  • the non-aqueous solvent may be a non-fluorinated carbonate (hereinafter referred to as "carbonate") and/or a fluorinated carbonate.
  • carbonates include, but are not limited to, cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate (BC); linear carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), ethyl methyl carbonate (EMC), methylpropyl carbonate (MPC) and ethylene propyl carbonate (EPC); and any of the above carbonates combination.
  • the fluorinated carbonate may be a fluorinated derivative of the above carbonates, such as fluoroethylene carbonate (FEC), difluoroethylene carbonate, and dimethyl difluorocarbonate (DFDMC). ).
  • the electrolyte may also contain a boron-based anion acceptor (ie, a boron-containing material that can accept anions).
  • a boron-based anion acceptor ie, a boron-containing material that can accept anions.
  • the boron-based anion acceptor is not particularly limited, and borane, borate ester and borate salt can be used as long as they have a Lewis acid center on the boron atom and can be combined with a pre-lithiation lithium source having a Lewis base center ( For example, Li 2 C 2 ) forms a complex.
  • the solubility of the pre-lithiation lithium source (for example, Li 2 C 2 ) in the electrolyte can be increased, and the power of the prelithiation lithium source to deintercalate lithium can be improved.
  • the electrolyte contains lithium salts is unstable to heat (e.g., LiPF 6)
  • a borane, a borate or borate anion can stabilize (e.g., PF 6 5-), and reduce the decomposition of the lithium salt.
  • the decomposition of the lithium salt causes capacity decay and increases resistance in the charge/discharge cycle.
  • a borane represented by the formula (fluoroalkyl-O) 3 -B a borane represented by the formula (fluoroaryl-O) 3 -B, and a formula (fluoroaryl) may be employed.
  • Borane represented by 3- B see HS Lee et al, J. Electochem. Soc., 145 (1998), pp. 2813-2818, which is incorporated herein by reference in its entirety.
  • Exemplary borate ester may include, but are not limited to, borate, tri (2H- hexafluoroisopropyl yl) ester (THFPB, [(CF 3) 2 CHO] 3 B) , and tri (2,4-difluoro-B ()) ester (F 2 C 6 H 3 O) 3 B.
  • Exemplary boranes can include, but are not limited to, tris(pentafluorophenyl)borane (TPFPB, (C 6 F 5 ) 3 B).
  • R is a fluorine-containing moiety.
  • oxalate boron oxalates may include, but are not limited to, pentafluorophenylboronoxalate (PFPBO).
  • Lithium bis(oxalato)borate represented by the following formula may also be used as a boron-based anion acceptor in the electrolyte:
  • lithium oxaltodifluoroborate (chemical formula LiBF 2 C 2 O 4 , abbreviated as LiODFB) described in US Pat. No. 10/625,686 can also be used as a boron-based anion acceptor in an electrolyte.
  • the oxalate boron oxalates (such as PFPBO), LiBOB, and LIODFB all contribute to the formation of a more stable SEI layer on the surface of the negative electrode, thereby reducing lithium consumption and improving battery performance.
  • NCM-111 lithium nickel cobalt manganese oxide, positive active material, D50: 12 ⁇ m, available from BASF.
  • Super P superconducting carbon black, carbon material, 40 nm, available from Timcal.
  • KS6L flake graphite, carbon material, about 6 ⁇ m, purchased from Timcal.
  • PVDF polyvinylidene fluoride, binder, available from Sovey.
  • NMP N-methyl-2-pyrrolidone, solvent, purchased from Sinopharm Chemical Reagent Co., Ltd.
  • Celgard 2325 polypropylene/polyethylene/polypropylene laminate film (PP/PE/PP film), separator, available from Celgard.
  • the obtained granules were placed in a cermet mold, and then the cermet mold containing the powder was immediately placed in a discharge plasma sintering furnace to be sintered again.
  • the external pressure was set to 300 MPa
  • the heating rate was set to 50 ° C / minute
  • the temperature was maintained for 2 minutes, thereby obtaining 72 mg of fine powder.
  • the obtained fine powder was subjected to XRD diffraction, and it was found that all the peaks were in agreement with the known Li 2 C 2 [JCPDS No. 70-3193].
  • NCM-111 938.6 mg NCM-111, 26.4 mg of the previously prepared Li 2 C 2 , 10 mg Super P, 5 mg KS6L, 20 mg PVDF were added to 450 mL. NMP. After stirring for 3 hours, the obtained uniformly dispersed slurry was applied onto an aluminum foil, followed by drying at 80 ° C for 6 hours in a vacuum. The coated aluminum foil was taken out from the glove box and punched into a plurality of 12 mm positive electrode sheets (abbreviated as NCM) using an EQ-T-06 battery pole piece punching machine (purchased from Shenzhen Weizhida Optoelectronics Technology Co., Ltd.). -Li 2 C 2 ).
  • NCM 12 mm positive electrode sheets
  • a coin battery (CR2016) was assembled using the positive electrode tab obtained above.
  • a pure lithium metal foil was used as the counter electrode.
  • 1 M LiPF 6 in FEC/EMC (3:7 by volume, a mixture of fluoroethylene carbonate (FEC) and ethyl methyl carbonate (EMC)) was used as the electrolyte.
  • Celgard 2325 (PP/PE/PP film) was used as the separator.
  • a positive electrode tab (abbreviated as NCM) was prepared in the same manner as in Example 1, except that Li 2 C 2 was not used, and 965 mg of NCM-111 was used instead of 938.6 mg of NCM-111.
  • Fig. 1 compares the charge/discharge performance of the battery prepared in Comparative Example 1 and Example 1 at the first charge/discharge cycle.
  • each battery was charged/discharged in a voltage range of 3-4.6 V (vs Li/Li + ).
  • the mass loading of NCM was about 10 mg/cm 2 .
  • the specific capacity is calculated based on the weight of the NCM.
  • the NCM-Li 2 C 2 positive electrode of Example 1 improved the charging capacity at the time of the first charge as compared with the NCM positive electrode of Comparative Example 1.
  • Figure 2 compares the cycle performance of Comparative Example 1 with the battery prepared in Example 1.
  • each battery is charged/discharged in a voltage range of 3-4.6 V (vs Li/Li + ); then, in the second to 80 charge/discharge cycles, 3
  • Each battery is charged/discharged within a voltage range of -4.3 V (vs Li/Li + ).
  • the mass loading of NCM was about 10 mg/cm 2 .
  • the specific capacity is calculated based on the weight of the NCM.
  • the NCM-Li 2 C 2 positive electrode in Example 1 showed improved capacity and stability as compared with the NCM positive electrode in Comparative Example 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
PCT/CN2017/072568 2017-01-25 2017-01-25 锂离子电池及其制备方法 WO2018137169A1 (zh)

Priority Applications (4)

Application Number Priority Date Filing Date Title
PCT/CN2017/072568 WO2018137169A1 (zh) 2017-01-25 2017-01-25 锂离子电池及其制备方法
CN201780075404.9A CN110036523A (zh) 2017-01-25 2017-01-25 锂离子电池及其制备方法
KR1020197021700A KR20190103232A (ko) 2017-01-25 2017-01-25 리튬 이온 배터리 및 그 제조 방법
DE112017006921.1T DE112017006921T5 (de) 2017-01-25 2017-01-25 Lithium-Ionen-Zelle und Verfahren zur Herstellung davon

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2017/072568 WO2018137169A1 (zh) 2017-01-25 2017-01-25 锂离子电池及其制备方法

Publications (1)

Publication Number Publication Date
WO2018137169A1 true WO2018137169A1 (zh) 2018-08-02

Family

ID=62977843

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/072568 WO2018137169A1 (zh) 2017-01-25 2017-01-25 锂离子电池及其制备方法

Country Status (4)

Country Link
KR (1) KR20190103232A (de)
CN (1) CN110036523A (de)
DE (1) DE112017006921T5 (de)
WO (1) WO2018137169A1 (de)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109103496A (zh) * 2018-08-24 2018-12-28 上海空间电源研究所 一种长贮存寿命锂离子电池及其制备方法
CN112038638A (zh) * 2020-09-01 2020-12-04 福建巨电新能源股份有限公司 一种锂离子正极材料补锂改性方法
CN112786866A (zh) * 2021-02-02 2021-05-11 衡阳市瑞启新能源有限公司 一种固态锂离子蓄电池负极及其制备方法
WO2021235818A1 (ko) * 2020-05-18 2021-11-25 주식회사 엘지에너지솔루션 이차전지의 제조방법
CN114586218A (zh) * 2020-01-20 2022-06-03 株式会社Lg新能源 制备二次电池的新方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112490518B (zh) * 2020-11-19 2022-07-08 欣旺达电动汽车电池有限公司 正极补锂添加剂及其制备方法、正极和锂离子电池
CN112768628A (zh) * 2021-02-05 2021-05-07 远景动力技术(江苏)有限公司 一种正极极片及其制备方法和应用
DE102022104630A1 (de) 2022-02-25 2023-08-31 Forschungszentrum Jülich GmbH Verfahren zur verbesserten Vorbeladung von Batterieelektroden mit Metallionen und vorbeladene Batterieelektroden mit verbesserten elektrischen Eigenschaften

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102290252A (zh) * 2011-04-27 2011-12-21 山西永东化工股份有限公司 一种利用超导电炭黑制造超级电容器及耦合器的方法
CN105161756A (zh) * 2015-09-28 2015-12-16 广西师范大学 一种具有电量耗尽预警功能的磷酸铁锂锂离子电池
CN105552344A (zh) * 2016-02-24 2016-05-04 中国科学院物理研究所 一种锂离子电池正极片、锂离子电池及其制备方法
CN106058168A (zh) * 2016-02-03 2016-10-26 万向A二三系统有限公司 一种预锂化锂离子二次电池正极材料

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120183866A1 (en) 2009-07-29 2012-07-19 Brookhaven Science Associates ,LLC Fluorinated Arylboron Oxalate as Anion Receptors and Additives for Non-Aqueous Battery Electrolytes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102290252A (zh) * 2011-04-27 2011-12-21 山西永东化工股份有限公司 一种利用超导电炭黑制造超级电容器及耦合器的方法
CN105161756A (zh) * 2015-09-28 2015-12-16 广西师范大学 一种具有电量耗尽预警功能的磷酸铁锂锂离子电池
CN106058168A (zh) * 2016-02-03 2016-10-26 万向A二三系统有限公司 一种预锂化锂离子二次电池正极材料
CN105552344A (zh) * 2016-02-24 2016-05-04 中国科学院物理研究所 一种锂离子电池正极片、锂离子电池及其制备方法

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109103496A (zh) * 2018-08-24 2018-12-28 上海空间电源研究所 一种长贮存寿命锂离子电池及其制备方法
CN114586218A (zh) * 2020-01-20 2022-06-03 株式会社Lg新能源 制备二次电池的新方法
EP4037019A4 (de) * 2020-01-20 2022-12-07 LG Energy Solution, Ltd. Neuartiges verfahren zum produzieren einer sekundärbatterie
CN114586218B (zh) * 2020-01-20 2023-12-12 株式会社Lg新能源 制备二次电池的新方法
WO2021235818A1 (ko) * 2020-05-18 2021-11-25 주식회사 엘지에너지솔루션 이차전지의 제조방법
CN112038638A (zh) * 2020-09-01 2020-12-04 福建巨电新能源股份有限公司 一种锂离子正极材料补锂改性方法
CN112786866A (zh) * 2021-02-02 2021-05-11 衡阳市瑞启新能源有限公司 一种固态锂离子蓄电池负极及其制备方法

Also Published As

Publication number Publication date
CN110036523A (zh) 2019-07-19
KR20190103232A (ko) 2019-09-04
DE112017006921T5 (de) 2019-10-02

Similar Documents

Publication Publication Date Title
WO2018137169A1 (zh) 锂离子电池及其制备方法
JP6203497B2 (ja) リチウム２次電池用正極活物質及びこれを含むリチウム２次電池
JP5882516B2 (ja) リチウム二次電池
TWI506838B (zh) Nonaqueous electrolyte storage battery and manufacturing method thereof
KR101378125B1 (ko) 리튬 이차 전지용 음극 활물질, 이의 제조 방법 및 이를 포함하는 리튬 이차 전지
US8628883B2 (en) Positive electrode for rechargeable lithium battery and rechargeable lithium battery including same
WO2015083900A1 (ko) 리튬 이차 전지용 양극 활물질, 이의 제조방법 및 이를 포함하는 리튬 이차 전지
US20090068560A1 (en) Non-aqueous electrolyte secondary battery
US9893348B2 (en) Positive active material for lithium secondary battery and lithium secondary battery
WO2015053586A1 (ko) 리튬 이차 전지용 양극 활물질, 이의 제조방법 및 이를 포함하는 리튬 이차 전지
WO2018112801A1 (en) Lithium ion battery and preparation method thereof
JP6441006B2 (ja) リチウムイオン電池用負極材料の製造方法
US9899668B2 (en) Method of preparing positive active material for rechargeable lithium battery, positive active material for rechargeable lithium battery prepared by method, and rechargeable lithium battery including same
US20200067129A1 (en) Lithium Ion Battery and Prelithiation Method of Anode
JP2016004708A (ja) リチウムイオン二次電池用正極活物質およびその製造方法、ならびにそれを用いたリチウムイオン二次電池
EP2985819A1 (de) Positiv aktives material für eine wiederaufladbare lithiumbatterie
WO2016186479A1 (ko) 리튬 이차 전지용 양극 활물질, 이의 제조방법 및 이를 포함하는 리튬 이차 전지
US20130183585A1 (en) Positive active material precursor for rechargeable lithium battery, method of preparing positive active material for rechargeable lithium battery using the same, and rechargeable lithium battery including the prepared positive active material for rechargeable lithium battery
JP5472952B1 (ja) 非水二次電池
KR20160058286A (ko) 리튬이온 이차전지
US20120135290A1 (en) Olivine-based positive active material for rechargeable lithium battery and rechargeable lithium battery using same
CN112204771A (zh) 制造硫碳复合物的方法、由此制造的硫碳复合物、包含所述硫碳复合物的正极和包含所述正极的锂二次电池
JP6296682B2 (ja) 正極活物質およびリチウム２次電池
WO2021060044A1 (ja) 硫黄変性ポリアクリロニトリルの製造方法
JP5659994B2 (ja) 負極活物質、リチウム二次電池、負極活物質の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17893957

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20197021700

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 17893957

Country of ref document: EP

Kind code of ref document: A1