WO2017216822A1 - Batteries au lithium-ion à charge rapide avec matériau d'anode revêtu de nano-carbone et électrolyte à sel de lithium à base d'anion imide - Google Patents

Batteries au lithium-ion à charge rapide avec matériau d'anode revêtu de nano-carbone et électrolyte à sel de lithium à base d'anion imide Download PDF

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WO2017216822A1
WO2017216822A1 PCT/JP2016/002850 JP2016002850W WO2017216822A1 WO 2017216822 A1 WO2017216822 A1 WO 2017216822A1 JP 2016002850 W JP2016002850 W JP 2016002850W WO 2017216822 A1 WO2017216822 A1 WO 2017216822A1
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lithium ion
carbon
ion battery
nano
lithium
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PCT/JP2016/002850
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Qian CHENG
Katsumi Maeda
Noriyuki Tamura
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Nec Corporation
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H01M2300/004—Three 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
    • H01M4/36—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention provides a new system for fast chargeable lithium ion batteries, with nano-carbon coated anode material, lithium transition metal oxide as cathode, and an electrolytic solution including imide anion based lithium salt electrolyte and lithium difluorophosphate.
  • Li-ion batteries have been widely used for portable electronics, and they are being intensively pursued for hybrid vehicles (HVs), plug-in hybrid vehicles (PHVs), electric vehicles (EVs), and stationary power source applications for smarter energy management systems.
  • HVs hybrid vehicles
  • PSVs plug-in hybrid vehicles
  • EVs electric vehicles
  • stationary power source applications for smarter energy management systems.
  • the greatest challenges in adopting the technology for large-scale applications are the energy density, power density, cost, safety, and cycle life of current electrode materials.
  • the charging time as well as the power density is the most important characteristics for the battery, especially as the application targets of Li-ion batteries move from small mobile devices to transportation. This is because EV users, for example, are hardly to wait more than half an hour to charge their vehicles during a long drive compared with a refueling period of less than 5 min for gasoline cars.
  • the speed of charge greatly depends on the lithiation rate capability of anode materials, cathode materials, electrolyte as well as solvent.
  • graphite is the most popular and practical anode material for Li-ion batteries because of its low cost, high capacity, relatively long cycle life, and ease of processing.
  • the small interlayer spaces 0.335nm
  • the lack of Li-ion intercalation sites on the natural graphite basal plane, and the long diffusion range among the graphite interlayers result in a limited lithiation rate capability of graphite anode materials.
  • Amorphous carbon such as soft carbon and hard carbon usually have larger interlayer spaces than graphite, offering a faster lithium input rate than graphite.
  • soft carbon usually has a limited capacity (around 250 mAh/g) and higher average potential while charging and discharging, it is difficult to be used in Li-ion batteries with high energy density.
  • Hard carbon has a capacity around 400 mAh/g, but its low density, low coulombic efficiency, and high cost make it difficult to use in batteries for EVs and PHVs at a low enough cost.
  • Other high capacity anode materials such as silicon and tin alloys have even worse lithiation rate capabilities because of the low kinetics of lithium alloying and the accessibility of lithium ion through thick SEI.
  • US2015/0014582 A1 tried to composite carbon with Li 4 Ti 5 O 12 for fast chargeable lithium ion batteries.
  • US2012/0021294 proposes a carbon core bonded with satellite parties to be used in the high-rate anode materials for lithium ion batteries.
  • they have not gotten an anode material satisfying fast charging capability, long cyclability, high capacity, high coulombic efficiency as well as easy processing, simultaneously.
  • a non-aqueous electrolytic solution is frequently used in current lithium ion battery industry.
  • mixed solvents of cyclic carbonate such as ethylene carbonate (EC) and propylene carbonate (PC)
  • linear carbonate such as dimethyl carbonate (DMC), diethyl carbonate (DEC) and ethyl methyl carbonate (EMC)
  • lithium salts such as LiPF 6 , LiBF 4 , LiN(SO 2 CF 3 ) 2 , LiN(SO 2 F) 2 , LiN(SO 2 C 2 F 5 ) 2 and Lithium bis(oxalate) borate (LiB(C 2 O 4 ) 2 ) for current lithium ion batteries.
  • JP2009-064574 discloses a double layer anode, which has a low rate layer comprising artificial graphite closer to a current collector and a high rate layer comprising natural graphite on the low rate layer.
  • JP2015-002122 discloses graphite particles covered with at least one material selected from (1) Si or Si compounds, (2) Sn or Sn compounds, and (3) soft carbons at the edge portion to increase the charging rate.
  • a new battery system is proposed with anode surface nano-carbon coating, imide anion based lithium salt included electrolyte with ternary solvent system, and electrolyte additives for high energy density and fast chargeable lithium ion batteries.
  • a lithium ion battery comprising: an anode comprising a carbon active particle and a nano-carbon additive having a pathway of lithium ions, and an electrolytic solution comprising imide anion based lithium salt and LiPO 2 F 2 .
  • B The lithium ion battery according to (A), wherein the surface of the carbon active particle is covered with the nano-carbon additive.
  • C The lithium ion battery according to (A) or (B), wherein the nano-carbon additive is selected from the group consisting of carbon nanotubes and porous graphenes.
  • (F) The lithium ion battery according to any one of (A) to (E), wherein the electrolytic solution comprises a composite of the imide anion based lithium salt and other lithium salt as an electrolyte and the mole ratio of the imide anion based lithium salt to the lithium salt is from 1/9 to 9/1.
  • (G) The lithium ion battery according to (F), wherein the total concentration of the electrolyte in the electrolytic solution is in the range of 0.1 to 3 moles/L.
  • (H) The lithium ion battery according to any one of (A) to (G), wherein the electrolytic solution comprises ethylene carbonate (EC), dimethyl carbonate (DMC) and ethyl methyl carbonate (EMC) as solvents, with the volume ratio of ED/DMC/EMC being x:y:100-x-y, where x is 15 to 50% by volume, y is 20 to 60% by volume and x+y is less than 100% by volume.
  • (I) The lithium ion battery according to any one of (A) to (H), wherein an amount of LiPO 2 F 2 is 0.005 to 7 wt% in the electrolytic solution.
  • (J) The lithium ion battery according to any one of (A) to (I), wherein the amount of the nano-carbon additive is in a range of 0.1 to 10 parts by weight per 100 parts by weight of the carbon active particle.
  • a fast chargeable lithium ion battery can be provided.
  • Fig. 1A shows a SEM image of the surface of the anode in Comparative Example 1.
  • Fig. 1A shows a SEM image of the surface of the anode in Comparative Example 1 at another magnitude.
  • Fig. 2A shows a SEM image of the surface of the anode in Example 3.
  • Fig. 2A shows a SEM image of the surface of the anode in Example 3 at another magnitude.
  • Fig. 3A shows a SEM image of the surface of the anode in Example 4.
  • Fig. 3A shows a SEM image of the surface of the anode in Example 4 at another magnitude.
  • Fig. 4A shows a SEM morphology of porous graphene.
  • Fig. 4B shows a TEM morphology of porous graphene.
  • Fig. 5 shows a cross-section image of the electrode in Example 1.
  • a lithium ion battery of one exemplary embodiment of the present invention includes a positive electrode (i.e., cathode) and a negative electrode (i.e., anode), and non-aqueous electrolytic solution.
  • This invention proposes a special combination of anode materials and electrolyte with additives to fabricate lithium ion batteries with fast chargeable capabilities.
  • the anode of the present invention includes a carbon active particle and a nano-carbon additive.
  • the carbon active particle can be selected from natural graphite, artificial graphite, soft carbon, hard carbon, MCMB, or their composition.
  • the shape of the carbon active particle can be spherical or flake. However, the spherical graphite particles are preferred since the compatibility of battery industry and ease of process.
  • the size of the carbon active particles can be in the range of 1 ⁇ m to 30 ⁇ m, 5 ⁇ m to 20 ⁇ m is more preferred, and 7 ⁇ m to 10 ⁇ m is most preferred. This is because the larger particle size will have a longer in-plane lithium ion diffuse distance when intercalation, that attribute to poor charge rate, in contrast, very small carbon particles, such as less than 1 ⁇ m will have a lot of edge plane which will have irreversible reactions with electrolyte at initial charge and discharge, which lead to low initial coulombic efficiency.
  • the specific surface area of the carbon particle is preferably to be controlled in the range of 1 m 2 /g to 15 m 2 /g so as to have an acceptable initial coulombic efficiency.
  • the carbon material can also have both pores on the surface and hollow or interconnected pores, or interconnected inside cracks at the core part of the graphite particles. Regarding to the definition of the core part, it is defined as the inner 70% of the volume of the carbon particles.
  • the nano-carbon additive of the present invention has a pathway of lithium ions such as holes, pores, pipes, tubes and the like.
  • the nano-carbon additive can adhere on the surface of the carbon active particle by simply mixed with both materials, for example, at the time of preparing an anode slurry.
  • the nano-carbon additive can be porous graphene.
  • the graphene can be single layered graphene or multi-layered graphene.
  • the multi-layered graphene has up to 200 layers. The few layer graphene with more than 200 layers will have much inconspicuous effect.
  • the graphene materials are activated with pores, the size of the pore is controlled between 70-200 nm. Too smaller pores ( ⁇ 70nm) will lead to greatly increase the surface area so that the coulombic efficiency will be decreased and the cycle life of the cell will be poor. It will be less effective if it has too larger pores which are larger than 200 nm.
  • the number of pores can be in the range of 10-500 pores per ⁇ m 2 .
  • the pores are advantageous for the transportation of lithium ions while charging and discharging. Otherwise, the graphene sheets will block or increase the lithium ion intercalation path in anode materials. However, the activated graphene with higher pore density (>500 pores/ ⁇ m 2 ) or lots of small pores ( ⁇ 70 nm) will decrease the coulombic efficiency.
  • the proposed activated graphene preferably has a low content of oxygen; the content of oxygen is preferably less than 0.8wt%. High oxygen content may cause a low coulombic efficiency and poor cycleability of the cell.
  • the proposed activated graphene can have a low crystallization for a high electrolyte absorption property and easy to disperse well in the slurry.
  • the pore volume of the porous graphene is important to the absorption of electrolyte and therefore, the pore volume is preferably in a range of 1.35 to 3 cm 3 /g.
  • This porous graphene has a sponge like structure and extremely low density. The density is preferably less than 0.3 g/cc.
  • the porous graphene can be further doped by boron or nitrogen with 0.1 to 5% by weight for better conductivity, better electrolyte absorption property and better dispersibility.
  • the porous graphene can be added to the anode slurry of 0.1-10wt%.
  • the SEM and TEM images of porous graphene are shown in Figs.4A and 4B, respectively.
  • Such a porous graphene can be obtained by the following procedures: 1) Graphite oxide, graphene oxide, expandable graphite, graphite intercalation compound can be used as the starting materials. 2) The materials described in step 1) are thermal shocked in air from room temperature to 250°C with a raising rate of 10°C/min or more to expand into graphene like structure. 3) The materials after step 2) are further heat treated in air at a temperature of 350°C to 850°C so as to have functional groups by oxidizing the surface. 4) The materials after step 3) are still further heat treated in N 2 atmosphere for 2 to 24h to make holes or pores on the surface of graphene.
  • CNTs carbon nanotubes
  • the length of the CNTs can be in a range of 5 nm to 50 ⁇ m.
  • the ultra-short CNTs cannot form a conductive network on the carbon active particles while ultra-long CNTs are hard to disperse in the electrode slurry.
  • the diameter of the CNTs is preferably 1.2 nm to 100 nm.
  • the purity of the CNT is preferably higher than 95%.
  • the surface area of the carbon nanotubes is preferably in a range of 10 to 300 m 2 /g.
  • the CNTs can be dispersed in water or N-methylpyrrolidone (NMP) or other solvent for the easy preparation of the electrode slurry.
  • concentration can be 10 % by weight in water or NMP.
  • Surfactant can be used to well disperse CNTs, especially in water based solution. Examples of the surfactants include octylphenol ethoxylate (Triton X-100, trade name, manufactured by Dow Chemicals), sodium dodecyl sulfate (SDS) and polyvinylpyrrolidone (PVP). To fabricate the CNT dispersions, 0.5-3 % by weight of the surfactant can be added.
  • the nano-carbon additive such as the porous graphene or the carbon nanotubes can form a conductive network on the surface of the carbon active particles, and as a result, the conductivity of the anode can increase so that the better rate performance can be attained.
  • the amount of nano-carbon additive is preferably in a range of 0.1 to 10 parts by weight per 100 parts by weight of the carbon active particles.
  • the cathode materials may be at least one material selected from the group consisting of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium vanadium oxide, lithium-mixed metal oxide, lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, lithium mixed metal phosphates, metal sulfides, and combinations thereof.
  • the positive electrode active material may also be at least one compound selected from chalcogen compounds, such as titanium disulfate or molybdenum disulfate.
  • lithium cobalt oxide e.g., Li x CoO 2 where 0.8 ⁇ x ⁇ 1
  • lithium nickel oxide e.g., LiNiO 2
  • lithium manganese oxide e.g., LiMn 2 O 4 and LiMnO 2
  • All these cathode materials can be prepared in the form of a fine powder, nano-wire, nano-rod, nano-fiber, or nano-tube. They can be readily mixed with an additional conductor such as acetylene black, carbon black, and ultra-fine graphite particles.
  • lithium-mixed metal oxide such as LiCo 0.8 Ni 0.2 O 2 , LiNi 0.4 Co 0.3 Mn 0.3 O 2 , LiNi 0.5 Co 0.2 Mn 0.3 O 2 , LiNi 0.5 Co 0.3 Mn 0.2 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 , LiNi 0.8 Co 0.15 Al 0.05 O 2 , Li 1.2 Mn 0.4 Ni 0.4 O 2 , Li 1.2 Mn 0.6 Ni 0.2 O 2 , Li 1.2 Mn 0.56 Ni 0.17 Co 0.07 O 2 , Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 , Li 1.2 Mn 0.56 Ni 0.17 Co 0.07 O 2 , Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 , Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 , LiNi 0.8 Co 0.15 Al 0.05 O 2 , LiNi 0.5 Mn 1.48 Al 0.02 O 4 , LiNi 0.4 Co 0.2 Mn 1.
  • the layered structure cathode materials can be used alone or in combination of two or more materials.
  • NCM523 can be combined with NCM811 with the ratio of 1:1 as cathode materials.
  • NCMabc such as NCM523 and NCM811 is an abbreviation of lithium-nickel-cobalt-manganese complex oxides where a, b and c are mole ratios of nickel, cobalt and manganese, respectively.
  • binder For the preparation of an electrode, binder is needed to be used for both anode and cathode.
  • the binder include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), ethylene propylene diene copolymer (EPDM), or styrene-butadiene rubber (SBR).
  • PTFE polytetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • EPDM ethylene propylene diene copolymer
  • SBR styrene-butadiene rubber
  • CMC carboxy methyl cellulose
  • Electrolytic solution includes an electrolyte, an additive and non-aqueous solvent.
  • the electrolytic solution of the present invention includes imide anion based lithium salt as the electrolyte and lithium difluorophosphate as the additive.
  • the electrolyte is preferably used as a composite of an imide anion based lithium salt such as lithium bis(fluorosulfonyl) imide (LiFSI) composed with a conventional lithium salt, such as lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ) et al.
  • LiFSI lithium bis(fluorosulfonyl) imide
  • LiPF 6 lithium hexafluorophosphate
  • LiBF 4 lithium tetrafluoroborate
  • the total concentration of the electrolyte can be in the range of 0.1 to 3 moles/L.
  • the range is preferable to 0.5 to 2 moles/L.
  • the mole ratio of the imide anion based lithium salt to the lithium salt can be selected from 1/9 to 9/1.
  • the use of the imide anion based lithium salt can have to a quick desolvation effect when intercalation, which attribute to faster charging rate than conventional electrolyte system.
  • pure ionic liquid such as LiFSI will etch the Al current collector at a full charged state; the use of composite electrolyte can effectively prevent the corrosion of Al current collector.
  • solvent A wide range of solvent can be used for lithium ion battery. Most preferred are non-aqueous and polymer gel electrolytes although other types can be used. Any known non-aqueous solvent which has been employed as a solvent for a lithium secondary battery can be employed. A mixed solvent comprising ethylene carbonate (EC) and at least one kind of non-aqueous solvent whose melting point is lower than that of ethylene carbonate and whose donor number is 18 or less may be preferably employed as the non-aqueous solvent.
  • EC ethylene carbonate
  • a mixed solvent comprising ethylene carbonate (EC) and at least one kind of non-aqueous solvent whose melting point is lower than that of ethylene carbonate and whose donor number is 18 or less may be preferably employed as the non-aqueous solvent.
  • This non-aqueous solvent is advantageous in that it is (a) stable against a negative electrode containing a carbonaceous material well developed in graphite structure; (b) effective in suppressing the reductive or oxidative decomposition of electrolyte; and (c) high ion conductivity.
  • a non-aqueous solvent solely composed of ethylene carbonate (EC) is advantageous in that it is relatively stable against decomposition although a reduction by a graphitized carbonaceous material.
  • the melting point of EC is relatively high, 39-40°C, and the viscosity thereof is relatively high, so that the conductivity thereof is low, thus making EC alone unsuited for use as a secondary battery electrolyte solvent to be operated at room temperature or lower.
  • the second solvent to be used in the mixed solvent with EC functions to make the viscosity of the mixed solvent lowering than that of which EC is used alone, thereby improving an ion conductivity of the mixed solvent. Furthermore, when the second solvent having a donor number of 18 or less (the donor number of ethylene carbonate is 16.4) is employed, the aforementioned ethylene carbonate can be easily and selectively solvated with lithium ion, so that the reduction reaction of the second solvent with the carbonaceous material well developed in graphitization is assumed to be suppressed. Further, when the donor number of the second solvent is controlled to not more than 18, the oxidative decomposition potential to the lithium electrode can be easily increased to 4 V or more, so that it is possible to manufacture a lithium secondary battery of high voltage.
  • Preferable second solvents are dimethyl carbonate (DMC), methyl ethyl carbonate (MEC), diethyl carbonate (DEC), ethyl propionate, methyl propionate, propylene carbonate (PC), ⁇ -butyrolactone ( ⁇ -BL), acetonitrile (AN), ethyl acetate (EA), propyl formate (PF), methyl formate (MF), toluene, xylene and methyl acetate (MA).
  • DMC dimethyl carbonate
  • MEC methyl ethyl carbonate
  • DEC diethyl carbonate
  • ethyl propionate methyl propionate
  • PC propylene carbonate
  • ⁇ -BL ⁇ -butyrolactone
  • AN acetonitrile
  • EA ethyl acetate
  • PF propyl formate
  • MF methyl formate
  • MA toluene
  • MA methyl acetate
  • the viscosity of this second solvent should preferably be 28 cps or less at 25°C.
  • the mixing ratio of the aforementioned ethylene carbonate in the mixed solvent should preferably be 10 to 80% by volume. If the mixing ratio of the ethylene carbonate falls outside this range, the conductivity of the solvent may be lowered or the solvent tends to be more easily decomposed, thereby deteriorating the charge/discharge efficiency. More preferable mixing ratio of the ethylene carbonate is 15 to 50% by volume. The larger content of EC will attribute to higher energy cost of desolvation which affects the charging speed. DMC and EMC are also included in this invention as a ternary solvent system of EC/DMC/EMC for better viscosity and ion conduction.
  • the volume ratio of EC/DMC/EMC is defined as x:y:100-x-y, where x is 15 to 50% by volume, y is 20 to 60% by volume and x+y is less than 100% by volume.
  • the volume ratio y of DMC is more preferably 30 to 50% by volume.
  • lithium difluorophosphate LiPO 2 F 2
  • LiPO 2 F 2 lithium difluorophosphate
  • 0.005-7wt% addition to the solvent is preferred; 0.01-5wt% is most preferred.
  • the decomposition of LiPO 2 F 2 can form a thin and highly conductive film on cathode materials that favorable to the fast charge and discharge capability.
  • the positive and negative electrodes can be formed by applying an electrode compound slurry on a current collector such as copper foil for the negative electrode and aluminum or nickel foil for the positive electrode.
  • the current collector can be deposited on a preformed electrode active layer by CVD, sputtering and the like. However, there is no particularly significant restriction on the type of the current collector, provided that the collector can smoothly path current and have relatively high corrosion resistance.
  • the positive and negative electrodes can be stacked with interposing a separator therebetween.
  • the separator can be selected from a synthetic resin nonwoven fabric, porous polyethylene film, porous polypropylene film, or porous PTFE film.
  • a casing for the battery in the exemplary embodiment may be, for example, a laminate film in which a substrate, a metal foil and a sealant are sequentially laminated.
  • a substrate which can be used include a resin film with a thickness of 10 to 25 ⁇ m made of polyester (PET) or Nylon.
  • a metal foil may be an aluminum film with a thickness of 20 to 40 ⁇ m.
  • a sealant may be a rein film with a thickness of 30 to 70 ⁇ m made of polyethylene (PE), polypropylene (PP), modified polypropylene (PP) or an ionomer.
  • Cathode LiNi 0.5 Co 0.2 Mn 0.3 O 2 was used as a cathode active material.
  • Cathode slurry was formulated by the weight ratio of the cathode active material: PVDF: carbon black as 89: 4: 7 and deposited on a 15 ⁇ m thick of Al current collector with the mass loading of 80g/m 2 .
  • the density of the cathode is controlled at 2.8g/cm 3 .
  • Anode Spherical natural graphite with the average diameter of 15 ⁇ m and specific surface area of 5 m 2 /g was used as anode active material.
  • the anode slurry was formulated by a weight ratio of active materials: CMC: SBR: carbon black as 92:2:2:4 and deposited on a 20 ⁇ m Cu foil with the mass loading of 45g/m 2 .
  • the density of the anode is controlled at 1.4g/cm 3 .
  • the morphology of the anode is shown in a SEM image of Fig. 1.
  • cathode and anode were laminated interposing porous polypropylene separator.
  • porous graphenes have the following properties: Number of layers: 5 layers as average Average pore size: 50 nm Number of pores on graphene layer: 12/ ⁇ m 2 O content: 0.5 wt% Pore volume: 2 cm 3 /g Specific surface area: 1050m 2 /g Raman peak intensity ratio I D /I G : 0.8
  • Example 1 was performed in the same manner as in Comparative Example 1 except for adding porous graphene obtained above (herein abbreviated as PG) to the anode slurry with the weight ratio of graphite: PG: CMC: SBR: carbon black as 91.7:0.3:2:2:4 and using an electrolytic solution as below.
  • the cross-section image of the electrode is shown in Fig.5.
  • Example 2 was performed in the same manner as in Example 1 except for changing the weight ratio of graphite: PG: CMC: SBR: carbon black as 91.5:0.5:2:2:4.
  • Example 3 was performed in the same manner as in Example 1 except for adding multi-wall carbon nanotubes (average diameter 10nm, specific surface area: 200m2/g, length: 500 nm, abbreviated as CNTs) and polyvinylpyrrolidone (PVP) as surfactant instead of PG to the anode slurry with the weight ratio of graphite: CNTs: PVP: CMC: SBR: carbon black as 86.949:3:0.051:2:2:4.
  • the morphologies of the anode are shown in Figs. 2A and 2B with the different magnitudes.
  • Example 4 was performed in the same manner as in Example 3 except for changing the weight ratio of graphite: CNTs: PVP: CMC: SBR: carbon black as 86.915:5:0.085:2:2:4.
  • the morphologies of the anode are shown in Figs. 3A and 3B with the different magnitudes.
  • Comparative Example 4 Comparative Example 4 was performed in the same manner as in Example 1 except for using vapor grown carbon fiber (VGCF, length: 10 ⁇ m, diameter: 150 nm) instead of PG to the anode slurry with the weight ratio of graphite: VGCF: CMC: SBR: carbon black as 89:5::2:2:4.
  • VGCF vapor grown carbon fiber
  • the charge rate capabilities of the samples are shown in Table 1.
  • the cells were charged to 4.2V in 1C, 4C, 6C, 10C and discharged to 2.5V in 0.1C. It can be learned the samples with the nano-carbon coated anode, the imide anion based lithium salt included electrolyte and the additive showed much better rate performance in high rate than the comparative samples.

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Abstract

L'invention concerne une batterie au lithium-ion, comprenant une anode comprenant une particule active de carbone et un additif de nano-carbone tel que des nanotubes et des graphènes poreux, et une solution électrolytique comprenant un sel de lithium à base d'anion imide et LiPO2F2. La solution électrolytique comprend de préférence un composite du sel de lithium à base d'anion imide et d'un autre sel de lithium comme électrolyte, et le rapport molaire du sel de lithium à base d'anion imide à l'autre sel de lithium est compris entre 1/9 et 9/1. De plus, la solution électrolytique comprend de préférence du carbonate d'éthylène (EC), du carbonate de diméthyle (DMC) et du carbonate d'éthyle méthyle (EMC) en tant que solvants, le rapport volumique de ED/DMC/EMC étant x:y:100-x-y, où x est de 15 à 50 % en volume, y est de 20 à 60 % en volume et x + y est inférieur à 100 % en volume.
PCT/JP2016/002850 2016-06-13 2016-06-13 Batteries au lithium-ion à charge rapide avec matériau d'anode revêtu de nano-carbone et électrolyte à sel de lithium à base d'anion imide WO2017216822A1 (fr)

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JP2018562687A JP6683265B2 (ja) 2016-06-13 2016-06-13 ナノカーボン被覆アノード材料およびイミドアニオン系リチウム塩電解質を有する高速充電可能なリチウムイオン電池

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WO2020195575A1 (fr) * 2019-03-28 2020-10-01 パナソニックＩｐマネジメント株式会社 Pile rechargeable à électrolyte non aqueux
WO2020203289A1 (fr) * 2019-03-29 2020-10-08 株式会社Ｇｓユアサ Électrolyte non aqueux pour élément de stockage d'énergie, élément de stockage d'énergie à électrolyte non aqueux, et procédé de production d'élément de stockage d'énergie à électrolyte non aqueux
CN113451581A (zh) * 2021-07-12 2021-09-28 珠海冠宇电池股份有限公司 一种负极片及包括该负极片的锂离子电池
CN114824438A (zh) * 2022-04-01 2022-07-29 宁波吉利罗佑发动机零部件有限公司 一种电池单体、动力电池、车辆辅助电池以及电池包

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JP2024510331A (ja) * 2021-03-15 2024-03-06 ビチュロセル カンパニー リミテッド 導電率及びイオン伝導性が向上したリチウム電池用電極の製造方法

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WO2020195575A1 (fr) * 2019-03-28 2020-10-01 パナソニックＩｐマネジメント株式会社 Pile rechargeable à électrolyte non aqueux
WO2020203289A1 (fr) * 2019-03-29 2020-10-08 株式会社Ｇｓユアサ Électrolyte non aqueux pour élément de stockage d'énergie, élément de stockage d'énergie à électrolyte non aqueux, et procédé de production d'élément de stockage d'énergie à électrolyte non aqueux
CN113451581A (zh) * 2021-07-12 2021-09-28 珠海冠宇电池股份有限公司 一种负极片及包括该负极片的锂离子电池
CN114824438A (zh) * 2022-04-01 2022-07-29 宁波吉利罗佑发动机零部件有限公司 一种电池单体、动力电池、车辆辅助电池以及电池包

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