WO2017168330A1 - Pile au lithium-ion - Google Patents

Pile au lithium-ion Download PDF

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Publication number
WO2017168330A1
WO2017168330A1 PCT/IB2017/051777 IB2017051777W WO2017168330A1 WO 2017168330 A1 WO2017168330 A1 WO 2017168330A1 IB 2017051777 W IB2017051777 W IB 2017051777W WO 2017168330 A1 WO2017168330 A1 WO 2017168330A1
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WIPO (PCT)
Prior art keywords
lithium
ion cell
current collector
cell according
contact fluid
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PCT/IB2017/051777
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English (en)
Inventor
Bartosz HAMANKIEWICZ
Andrzej CZERWIŃSKI
Michał KRAJEWSKI
Monika MICHALSKA
Ludwika LIPIŃSKA
Janusz Kozakiewicz
Jarosław PRZYBYLSKI
Krystyna SYLWESTRZAK
Witold SARNA
Original Assignee
Uniwersytet Warszawski
Instytut Technologii Materiałów Elektronicznych
Instytut Chemii Przemysłowej
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Publication of WO2017168330A1 publication Critical patent/WO2017168330A1/fr

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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
    • 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
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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
    • 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
    • H01M4/50—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
    • 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 object of the invention is a lithium-ion cell with an increased safety level, comprising a polymer separator serving the function of a solid electrolyte.
  • accumulators Three main types of accumulators are currently present in the market: lithium-ion, nickel-metal hydride and lead-acid. Each of those types of accumulators has its advantages allowing a specific application.
  • the use of nickel-cadmium accumulators was recently discontinued due to the high toxicity of cadmium.
  • Lead-acid accumulators are characterised by an operating voltage of 2.0-2.2 V. Lead-acid accumulators are a reliable and still the cheapest source of the acquired energy. Due to the very heavy weight of lead components, lead-acid accumulators are used only in devices for which the total mass increase does not constitute a significant problem, e.g. starter accumulators in combustion vehicles. Lead-acid accumulators are being considered as power sources for hybrid and electric cars (e.g. Ford). The greatest limitation of lead-acid accumulators is their large mass resulting from the necessity to use lead - one of the heaviest elements.
  • Nickel-metal hydride accumulators have an electromotive force of 1 .2-1 .3 V. Ni-MH accumulators feature good power parameters and their weight does not prevent them from being used in mobile devices. Due to this, nickel-metal hydride accumulators are used in mobile devices requiring high current densities, like e.g. photographic cameras, flash units. Nickel-metal hydride accumulators are also used to power hybrid cars provided with electric motors (e.g. Toyota Prius). The greatest limitation of nickel-metal hydride accumulators is their relatively low resistance to consecutive charging and discharging cycles.
  • Lithium-ion accumulators are characterised by an operating voltage of 3.2-4.0 V.
  • the lithium-ion cells reaching the highest powers have power capacities comparable with nickel-metal hydride accumulators.
  • Lithium-ion accumulators due to their very small mass, are used mainly to power mobile devices requiring low power, e.g. mobile telephones and laptops.
  • Lithium-ion accumulators are currently being comprehensively studied with respect to their huge development potential. They have the highest known capacity resulting from the use of lithium cations (the lightest metal) as a charge carrier.
  • Liquid electrolytes known from state of the art are volatile and flammable.
  • lithium-ion cells which use various substances for the construction of a positive electrode and a negative electrode, various substances for the construction of separators and various substances constituting the electrolyte.
  • Classic solutions comprise a negative electrode (anode when discharged) made of carbon material (e.g. lithium intercalated in graphite) and a positive electrode (cathode when discharged) made of transition metal oxides: lithium-cobalt LCO, lithium-nickel- manganese-cobalt NMC, lithium ferrophosphate LFP or lithium manganese oxide LMO with the formula LiMn 2 0 4 hinderLithium Batteries Science and Technology", Springer 2003).
  • Lithium titanium oxide with a spinel structure Li 4 Ti 5 0i 2 may be used in a lithium-ion cell as an anode with a specific capacity of approx. 1 70 mAh/g.
  • the high potential of reversible intercalation of lithium in its structure (approx. 1 .5 V in relation to metallic lithium) causes the chemical activity of Li + in the LTO matrix to be significantly lower than in carbon material.
  • the graphite anode there is no decomposition of the components of the electrolyte on titanate grains during first charging.
  • Mn 2+ ions always present in the electrolyte of the cell comprising manganese materials, do not undergo electrochemical reduction on the surface of LTO and do not affect the course of processes taking place in the battery in subsequent working cycles.
  • the above-mentioned advantages cause the LTO/LMO cell to be characterised by much more stable work, a lower decrease in the capacity during subsequent cycles of charging/discharging, a more predictable stoichiometry of the reactions which take place and the possibility of longer storage when charged. As a result, the operational safety of this type of lithium-ion batteries increases.
  • LTO/LMO type lithium-ion cell comprising a negative electrode made of lithium titanium oxide LTO with a spinel structure and the formula Li 4 Ti 5 0i 2 and a positive electrode of LMO (J. Electrochem. Soc, 141 (1994) L147; J. Electrochem. Soc, 142 (1995) 2558).
  • LTO is characterised by a crystallographic structure enabling reversible intercalation/deintercalation of three moles of lithium onto the formula of the compound translating into a theoretical specific capacity of 168 mAh/g.
  • liquid electrolyte is used in the form of 1 M of LiCI0 4 solution in propylene carbonate, being a volatile flammable material.
  • An LTO/LMO type lithium-ion cell is known, which uses liquid electrolyte comprising LiPF 6 dissolved in a mixture of ethylene carbonate and dimethyl carbonate (LiPF 6 @EC/DMC) (J. Power Sources, 83 (1999) 1 56).
  • the LTO/LMO cell in a coin-shaped form (CR2032) is characterised by an initial capacity of approx. 1 12 mAh/g (per the mass of cathode material) and loses 14% of its value during 50 cycles of charging/discharging.
  • LTO/LNMO type lithium-ion cell comprising a negative electrode of LTO and a positive electrode made of lithium manganese oxide substituted with nickel ions LiNi 0! 5Mn l !5 O 4 (LNMO) using a liquid electrolyte LiPF 6 @EC/DMC ⁇ Chem.
  • LNMO lithium manganese oxide substituted with nickel ions LiNi 0! 5Mn l !5 O 4
  • the LTO/LNMO cell is characterised by a capacity of 47.6 mAh/g (per the total mass of cathode and anode material) with a current load of 1 C.
  • the battery does not exhibit a significant decrease in capacity with a higher load.
  • An LTO/LAMO type lithium-ion cell comprising a negative electrode of LTO and a positive electrode made of LMO substituted with aluminium ions Li 1 i1 AI 0i1 Mn 1 i8 O 4 (LAMO).
  • LAMO aluminium ions
  • this system it is possible to use numerous types of liquid electrolytes.
  • the specific capacity amounts to approx. 102 mAh/g (per the mass of cathode material) with a current load of 1 C and exhibits high resistance to charging/discharging cycles (Electrochem. Solid State Lett., 9 (2006) A557).
  • An LTO/LMO type lithium-ion cell is known with bipolar electrodes and liquid electrolyte comprising LiBF 4 dissolved in acetonitrile (J. Power Sources, 186 (2009) 508).
  • the layout of the arrangement of individual half-cells looks as follows:
  • the construction of the cell forced the use of an LMO electrode with twice as high capacity compared to LTO.
  • the authors used active materials with 3-D morphology and spherical grains less than 10 ⁇ in diameter. This procedure enabled the creation of compounds with a synergic effect of decreased dissolution of manganese in the electrolyte (due to its small specific surface) and fast diffusion of Li + ions (due to the short path of the movement of lithium in the original grains).
  • the electrodes comprised large amounts of carbon and binding agents, due to which the amount of active compound in the electrode mass amounted to just 65%. In spite of this, the presented battery is characterised by high specific energy.
  • An LTO/LMO type lithium-ion cell is known with LiPF 6 @EC/DMC liquid electrolyte using electrode materials with bipartite morphology (Adv. Mater., 22 (2010) 3052).
  • the grains with diameters below 10 nm form agglomerates 0.5-2 ⁇ in size.
  • the cells exhibit a nominal capacity of 2-5 Ah and considerable resistance to high discharge currents.
  • An LTO/LMO type hybrid lithium-ion cell is known with LiBF 4 @EC/DMC/EMC liquid electrolyte in a cell- capacitor system (J. Power Sources, 187 (2009) 635).
  • the positive electrode comprises approx. 30% of the mass of LiMn 2 0 4 and 45% of acetylene black serving the function of a supercapacitor.
  • the cell is characterised by a specific energy of 10 Wh/kg with a direct current discharge and exhibits a slight decrease in the specific capacity amounting to 0.001 6%/cycle.
  • An LTO/LMO type lithium-ion cell is known with a liquid PC/EMC electrolyte comprising lithium salt Li 2 B 12 F )( H 1 2 ⁇ J. Power Sources, 195 (2010) 1479).
  • the cell is characterised by high specific capacity of approx. 120 mAh/g (per the mass of cathode material), however, after 25 cycles it retains only 76% of the original capacity.
  • An LTO/LMO type lithium-ion cell is known with a solid polymer electrolyte consisting of polyacrylonitrile (PAN) saturated with LiPF 6 @EC/DMC, which constitutes 79 mol% of the electrolyte (J. Electrochem. Soc, 145 (1998) 2615). Although the separator has been classified by the authors as a solid electrolyte, the considerable amount of volatile components should be noted. The battery exhibits a nominal capacity of 4.73 mAh.
  • An LTO/LMO type lithium-ion cell is known with a solid electrolyte based on poly(ethylene oxide) PEO and polyethylene glycol (PEG) (Solid State Ionics, 144 (2001 ) 1 85).
  • PEG polyethylene glycol
  • Solid State Ionics, 144 (2001 ) 1 85 In order to improve the ionic conductivity, a considerable amount of PEG with LiTFSI salt was added to the electrode masses, which unfortunately decreases the active mass content down to 60%.
  • the system is characterised by a capacity of approx. 100 mAh/g (per the mass of cathode material) in an elevated operating temperature (40°C), which unfortunately decreases almost by half in room temperature.
  • An LTO/LMO type lithium-ion cell is known with a solid gel electrolyte made of poly(vinylene fluoride) (PVDF) saturated with a standard liquid electrolyte LiPF 6 @EC/DMC (J. Electrochem. Soc, 152 (2005) A1949).
  • PVDF poly(vinylene fluoride)
  • LiPF 6 @EC/DMC LiPF 6 @EC/DMC
  • a disadvantage of a LTO/PVDF/LMO button cell constructed in such a manner is the earlier activation of the negative electrode in the system with metallic lithium.
  • the system is characterised by high specific capacity of approx. 130 mAh/g (per the mass of active material), but low resistance to high density currents and a 0.2% capacity decrease in each cycle.
  • An aluminium current collector undergoes electrodissolution above a potential of 3.5 V in relation to the lithium electrode.
  • fluorinated inorganic anions in electrolytes comprising such salts as, e.g. LiPF 6 , LiBF 4 etc.
  • this collector undergoes passivation creating a stable layer of aluminium fluoride preventing a progressive degradation.
  • other lithium salts such as e.g. lithium bis(trifluoromethylsulphonyl)imide, LiTFSI
  • the aluminium collector undergoes constant oxidation reactions, which causes a gradual degradation of the cell and a decrease in its cyclic resistance.
  • additives ensuring the passivation of aluminium should be used.
  • One of such compounds is lithium bisoxalatoborate, LiB(C 2 0 4 ) 2 (abbreviation : LiBOB) (J. Power Sources, 296 (2015) 197).
  • LiPF 6 is used as the charge carrier, which at the same time causes the passivation of the aluminium charge carrier, ensuring its stabilisation.
  • a disadvantage of LiPF 6 is its extreme reactivity in relation to humidity. LiPF 6 in contact with humidity generates hydrogen fluoride (HF), which causes the dissolution of the individual components of the cell leading to a decrease in its cyclic resistance and current efficiency. Furthermore, hydrogen fluoride is extremely dangerous for organisms. The presence of volatile organic solvents in lithium-ion cells has always caused concerns regarding the safety of their use. Constructions with electrolyte contents above 1 ml/cm 2 in relation to the surface of the electrodes are used in state of the art.
  • the solution according to the present invention solves problems and inconveniences known from state of the art - it allows the creation of a safely operated lithium-ion accumulator, comprising a modern polymer separator serving the function of a solid electrolyte and minimum amounts of a non-volatile contact fluid, exhibiting the inability to emit hydrogen fluoride.
  • the solution according to the present invention is characterised by high power.
  • a lithium-ion cell comprising a negative electrode applied to an aluminium charge collector, a positive electrode applied to an aluminium charge collector, a polymer separator serving the function of a solid electrolyte, a steel spacer, a disc spring, a seal, a housing, a contact fluid, an ion charge carrier and a charge collector stabiliser is characterised in that the negative electrode applied to an aluminium current collector is made of lithium titanium oxide, the positive electrode applied to an aluminium current collector is made of lithium manganese oxide, the polymer separator serving the function of a solid electrolyte is made of silicone-urethane prepolymer, the contact fluid constitutes a solution in dimethyl carbonate.
  • the lithium-ion cell according to the invention is characterised in that lithium titanium oxide, Li 4 Ti 5 0 12 with a spinel structure for the construction of the negative electrode constitutes the product of a mechanochemical reaction of lithium oxide and titanium(IV) oxide in a molar ratio of 4:5, which mechanochemical reaction was conducted in a planetary ball mill, in the environment of ethyl alcohol for a minimum of 12 hours, preferably for 24 hours, using zirconium oxide balls with a diameter of 10 mm, and in the further stage the grinding product is subjected to a heating process in a two-stage regime, i.e. for 1 -5 hours in a temperature of 400-600°C, preferably 3 hours in a temperature of 500°C and subsequently for 10-30 hours in a temperature of 650-900°C, preferably for 20 hours in a temperature of 800°C.
  • the lithium-ion cell according to the invention is characterised in that the packing density of the electrode mass of the negative electrode on the current collector amounts to 1-5 mg/cm 2 , preferably 3 mg/cm 2 .
  • the lithium-ion cell according to the invention is characterised in that lithium manganese oxide, Li(Mn 2 0 4 ) for the construction of the positive electrode constitutes a product of a sol-gel reaction between lithium acetate and manganese acetate in a molar ratio of 1 :2, with 2-hydroxypropane-1 ,2,3-tricarboxylic acid, ethanoic acid, 2-hydroxyethanoic acid, ethane-1 ,2-diol having been used as a complexing agent, and subsequently having subjected the product of the reaction to heating in a temperature of 450-700°C with a temperature increase rate of 5°C/min, after which isothermal heating took place in a temperature of 700°C.
  • the lithium-ion cell according to the invention is characterised in that the packing density of the electrode mass of the positive electrode on the current collector amounts to 1-5 mg/cm 2 , preferably 3 mg/cm 2 .
  • the lithium-ion cell according to the invention is characterised in that a polymer separator is created in the process of hardening the mixture of a silicone-urethane prepolymer comprising polysiloxane and poly(oxyethylene) segments, along with lithium salt (LiTFSI - LiN(CF 3 S0 2 )2) and an ionic liquid with N- butyl N-methylpyrrolidinium bis(trifluoromethylsulphonyl)amide (PYR 14 TFSI).
  • the lithium-ion cell according to the invention is characterised in that the contact fluid content of the cell amounts to below 100 ⁇ /cm 2 in relation to the surfaces of the electrodes, preferably below 10 ⁇ /cm 2 in relation to the surfaces of the electrodes.
  • the contact fluid comprises a charge carrier in the form of lithium bis(trifluoromethylsulphonyl)imide (LiTFSI) in a concentration of 0.1 -1 .5 mol/l, preferably 0.8 mol/l.
  • the contact fluid comprises a current collector stabiliser in the form of lithium oxalatoborate (LiBOB) in a concentration of 0.05-0.5 mol/l, preferably 0.2 mol/l.
  • fig. 1 presents a layout of the system and the mutual positioning of the negative electrode (1 ) applied to an aluminium current collector (5), the positive electrode (2) applied to an aluminium current collector (5), the polymer separator (3) serving the function of a solid electrolyte with the contact fluid (4) applied to the surface in the lithium-ion cell prior to its assembly;
  • fig. 2 presents the results of the test of the lithium-ion cell according to the invention in a button system from an embodiment: a) galvanostatic charging of the cell; b) galvanostatic discharging of the cell; c) current efficiency of the cell ;
  • fig. 3 presents powder diffractograms of lithium titanium oxide used in the construction of the negative electrode, generated for various durations of grinding : a) 12 hours, b) 18 hours, c) 24 hours, d) 30 hours;
  • fig. 4 presents SEM photographs of lithium titanium oxide used in the construction of the negative electrode, generated for various durations of grinding: a) 12 hours, b) 1 8 hours, c) 24 hours, d) 30 hours;
  • fig. 5 presents a powder diffractogram of lithium manganese oxide used in the construction of the positive electrode;
  • fig. 6 presents SEM photographs of lithium manganese oxide used in the construction of the positive electrode magnified: a) 5000 times, b) 10000 times, c) 20000 times, d) 50000 times;
  • fig. 7 presents the structure of the silicone-urethane prepolymer used to generate polymer membranes, where U stands for urethane group, POE - poly(oxyethylene) chain, rectangle - diisocyanate skeleton, broken line - poly(siloxanodiol) chain, NCO - isocyanate group;
  • fig. 8 presents the results of a thermogravimetric measurement of the silicone-urethane prepolymer used to create polymer membranes, marking the glass transitions of the polymer in temperatures below - 125.59°C, -73.77°C and -39.58°C.
  • the negative electrode was made of lithium titanium oxide (LTO), created using the method of mechanochemical synthesis in the solid phase.
  • LTO lithium titanium oxide
  • the grinding was conducted in a planetary (ball) mill, in the environment of ethyl alcohol for 24 hours using balls made of zirconium oxide with a diameter of 10 mm.
  • the product of grinding is subjected to the process of heating in properly selected temperature and time conditions and atmosphere, i.e. 500°C for 3 hours and 800°C for 20 hours ⁇ Powder Technology, 266 (2014) 372-377).
  • lithium titanium oxide Li 4 Ti 5 0 12
  • the material exhibits an increase in the capacity for various discharge currents and resistance to high-current tests in relation to other materials of this class. This is particularly significant for the operation of the whole system.
  • the electrode material described herein synthesised in the above-mentioned manner has not been previously used for the construction of lithium-ion cells.
  • the positive electrode was made of lithium manganese oxide (LMO), created using a modified sol-gel method.
  • LMO lithium manganese oxide
  • the developed technology allowed obtaining single-phase materials (with no foreign phases like e.g. manganese oxides) in an amount of 100 g per one synthesis with an efficiency of approx. 96%.
  • 2-hydroxypropane-1 ,2,3-tricarboxylic acid was introduced into this synthesis as a complexing agent.
  • other compounds were also introduced, like, e.g.
  • the active material Li 4 Ti 5 0 12 in the case of the negative electrode and LiMn 2 0 4 in the case of the positive electrode
  • a conductive additive Vulcan XC72R carbon
  • Adhesive is dripped into this mixture in an amount of 12-40 mg in the form of a 5% poly(vinylene fluoride) solution (PVDF) dissolved in 1 -methyl-2-pyrrolidone (NMP). 20-50 mg of NMP solvent are dripped into such a suspension in order to obtain proper viscosity of the paste.
  • PVDF poly(vinylene fluoride) solution
  • NMP 1 -methyl-2-pyrrolidone
  • the current collector is made of aluminium.
  • the stability of aluminium in the operating potential of the lithium-ion cell is ensured by adding LiBOB to the contact fluid.
  • the thickness of the current collector ranges between 10 and 50 pm.
  • Properly prepared electrode material is applied to the surface of the current collector and is subsequently uniformly spread by means of an automatic applicator with an aperture size of 50-250 pm.
  • the surplus of NMP solvent was removed from the layer prepared in such a manner by drying it in a temperature of 30-70°C in the air for 1-3 hours and subsequently in a temperature of 100-150°C under the vacuum for 10-15 hours.
  • the packing density of the electrode layer amounts to 1-5 mg/cm 2 .
  • electrodes with sizes adjusted to their specific use are cut from the material prepared in such a manner.
  • the electrodes are additionally dried in a temperature of 100- 150°C under the vacuum for 10-20 hours.
  • a new type of polymer separator described in patent application P.413615 is used for the construction of the cell.
  • the lithium-ion cell according to the invention is the first described construction using this type of polymer separator.
  • the polymer separator serves the function of a solid electrolyte.
  • the synthesis of the polymer used as a solid electrolyte in the cell according to the invention involved hardening the mixture of a silicone-urethane prepolymer comprising polysiloxane and poly(oxyethylene) segments, along with lithium salt (LiTFSI - LiN(CF 3 S0 2 )2) and an ionic liquid with N-butyl N-methylpyrrolidinium bis(trifluoromethylsulphonyl)amide (PYR 14 TFSI).
  • the polymer separator has a number of advantages in relation to state of the art. It is characterised by very good mechanical strength preventing its breakage during installation in the cell. It is also characterised by very high ionic conductivity, enabling fast diffusion of lithium ions while charging and discharging the cell.
  • the specific conductance of a polymer separator approx. 30 pm in thickness amounts to 1 .26-10 3 S/cm and it has been determined by means of the EIS method. Thermogravimetric studies have proved that the polymer exhibits three glass transition temperatures, the lowest (below -120°C) corresponding to glass transition in the silicone phase and the remaining ones (-74°C and -30°C) to glass transitions in the organic phase.
  • the polymer separator is characterised by its conductivity as well as thermal and mechanical properties appropriate for use in a lithium-ion cell.
  • the contact fluid improving the ionic contact of electrodes with the polymer separator and ensuring conductivity inside the pores of the electrodes is also a component of the cell.
  • the contact fluid constitutes a solution of LiTSI (lithium bis(trifluoromethylsulphonyl)imide) and LiBOB (lithium oxalatoborate) with a concentration of 0.2 mol/l in dimethyl carbonate (DMC).
  • the solution exhibits low vapour pressure and is stable under the working conditions of the cell.
  • the contact fluid is introduced into the cell directly before its assembly and hermetic sealing. The introduction of the contact fluid takes place by dripping it over both surfaces of the polymer separator, which tightly adheres to the surfaces of the electrodes.
  • the contact fluid is introduced while assembling the cell just before its closure.
  • the addition of the contact fluid is used in an amount of no more than 10 ⁇ /cm 2 in relation to the surfaces of the electrodes.
  • DMC serves the function of a dispersing phase
  • LiTFSI serves the function of a charge carrier
  • LiBOB serves the function of an agent stabilising the aluminium charge collector.
  • the ionic conductivity of LiTFSI is comparable to LiPF 6 , however, LiTFSI has been chosen due to its stability in the presence of trace humidity, which translates into the safety of operation for the whole cell.
  • LiBOB - this compound was chosen due to its stability in the operating conditions of the cell (with an operating voltage of approx. 2.5 V) and resistance in relation to humidity.
  • LTO/LMO lithium-ion cells using LiBOB have not been previously known.
  • the lithium-ion cell according to the invention is characterised by a specific energy of approx. 120 Wh/kg calculated per electrode masses and a cyclic resistance of approx. 55% after 50 cycles of deep charging/discharging.
  • the lithium-ion cell according to the invention exhibits an increased safety level due to the extremely low amount of fluidic components, which translates into the low amount of volatile components which can cause an increase in pressure inside the cell during its operation.
  • the only fluidic substance in the cell according to the invention is the contact fluid in an amount of less than 10 ⁇ /cm 2 in relation to surface electrodes.
  • the lithium-ion cell according to the invention exhibits an increased safety level also due to the use of stable and non-reactive substances serving the function of a charge carrier (LiTFSI) and a current collector stabiliser (LiBOB).
  • LiTFSI charge carrier
  • LiBOB current collector stabiliser
  • the lithium-ion cell in a button system has been made using LTO and LMO electrodes as well as a solid polymer electrolyte.
  • the positive and negative electrodes were created using a paste method on an aluminium collector (doctor blade slurry coating method).
  • the active material Li 4 Ti 5 0 12 in the case of the negative electrode and LiMn 2 0 4 in the case of the positive electrode
  • the active material Li 4 Ti 5 0 12 in the case of the negative electrode and LiMn 2 0 4 in the case of the positive electrode
  • a conducting additive Vulcan XC72R carbon
  • Adhesive was dripped into this mixture - poly(vinylene fluoride) (PVDF) in an amount of 25 mg, dissolved in the solvent - 1 -methyl-2-pyrrolidone (NMP) with a concentration of 5 wt%.
  • Electrodes with a diameter of 12 mm and geometric surface of 1 .13 cm 2 were subsequently cut from the layer and then dried in a temperature of 120°C under the vacuum for 1 5 h. After this operation, the electrodes were transferred to a glovebox with argon atmosphere, with humidity and oxygen content below 5 ppm, where they were used to construct a coin- shaped lithium-ion battery (coin cell) CR2032.
  • the negative electrode with a mass of 1 1 mg made of lithium titanium oxide with a spinel structure Li 4 Ti 5 0 12 was placed on the lower housing of the coin-shaped battery.
  • a separator 19 mm in diameter was cut from a layer of polyurethane separator and placed on the negative electrode.
  • the contact fluid was applied to it in an amount of 30 ⁇ of lithium salt solution (LiTFSI and LiBOB) with a concentration of 0.2 mol/dm 3 (in relation to LiBOB) dissolved in dimethyl carbonate (DMC).
  • a positive electrode with a mass of 13 mg was applied to this system, made of lithium manganese oxide with a spinel structure LiMn 2 0 4 .
  • a steel spacer, a disc spring and an upper housing (positive pole) were placed on a system of two electrodes separated by a polyurethane membrane.
  • the battery prepared in such a manner was compressed on a special press under a pressure of 150 bar for 20 s.
  • the battery ready for measurements weighed approx. 3.2 g.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Inorganic Chemistry (AREA)
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  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
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Abstract

L'invention concerne une pile au lithium-ion comprenant une électrode négative appliquée à un collecteur de courant en aluminium, une électrode positive appliquée à un collecteur de courant en aluminium, un séparateur de polymère ayant la fonction d'un électrolyte solide, un joint d'étanchéité, un boîtier, un fluide de contact, un porteur de charge d'ions et un stabilisateur de collecteur de charge, qui est caractérisée en ce que l'électrode négative (1) appliquée à un collecteur de courant en aluminium (5) est constituée d'oxyde de lithium et de titane (LTO), l'électrode positive (2) appliquée à un collecteur de courant en aluminium (5) est constituée d'oxyde de lithium et de manganèse (LMO), le séparateur de polymère (3) ayant la fonction d'un électrolyte solide est constitué de prépolymère de silicone-uréthane, et le fluide de contact (4) constitue une solution dans du carbonate de diméthyle. Le fluide de contact (4) comprend un porteur de charge sous forme de LiTFSI et un stabilisateur de collecteur de courant sous la forme de LiBOB. La teneur en fluide de contact (4) de la pile s'élève à une valeur inférieure à 1 0 μl/cm2 par rapport aux surfaces des électrodes. La pile au lithium-ion selon l'invention est caractérisée par une énergie spécifique d'approximativement 120 Wh/kg calculée par masses d'électrode et une résistance cyclique d'approximativement 55 % après 50 cycles de charge/décharge profonde. La pile au lithium-ion selon l'invention présente un niveau de sécurité accru dû à la quantité extrêmement faible de substances fluidiques et due à l'utilisation de substances stables et non réactives servant de porteur de charge et de stabilisateur de collecteur de courant.
PCT/IB2017/051777 2016-03-31 2017-03-28 Pile au lithium-ion WO2017168330A1 (fr)

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CN113363419A (zh) * 2021-06-23 2021-09-07 天津市捷威动力工业有限公司 一种负极极片及其制备方法和应用

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Publication number Priority date Publication date Assignee Title
FR3102889A1 (fr) 2019-10-30 2021-05-07 Saft Electrolyte gelifie pour element electrochimique lithium-ion
CN113363419A (zh) * 2021-06-23 2021-09-07 天津市捷威动力工业有限公司 一种负极极片及其制备方法和应用

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