WO2017193571A1 - 一种锂离子电池用导电粘结剂及其制备方法、锂离子电池电极极片及制备方法和锂离子电池 - Google Patents

一种锂离子电池用导电粘结剂及其制备方法、锂离子电池电极极片及制备方法和锂离子电池 Download PDF

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WO2017193571A1
WO2017193571A1 PCT/CN2016/108780 CN2016108780W WO2017193571A1 WO 2017193571 A1 WO2017193571 A1 WO 2017193571A1 CN 2016108780 W CN2016108780 W CN 2016108780W WO 2017193571 A1 WO2017193571 A1 WO 2017193571A1
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binder
ion battery
lithium ion
graphene
conductive
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PCT/CN2016/108780
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English (en)
French (fr)
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王志勇
夏圣安
王平华
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华为技术有限公司
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Priority to EP16901526.0A priority Critical patent/EP3444881B1/en
Publication of WO2017193571A1 publication Critical patent/WO2017193571A1/zh
Priority to US16/189,432 priority patent/US11024873B2/en

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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
    • 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
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • 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
    • 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
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the invention relates to the field of lithium ion batteries, in particular to a conductive binder for a lithium ion battery, a preparation method thereof, a lithium ion battery electrode pole piece, a preparation method thereof and a lithium ion battery.
  • Lithium-ion batteries have been widely used in portable electronic devices, electric vehicles, energy storage appliances, etc. due to their high energy density, long cycle life, and maintenance-free.
  • the existing lithium ion battery preparation process is to disperse the active material (positive or negative active material) powder, the conductive agent and the binder in a solvent into a slurry, and then apply it to a current collector (such as copper foil and aluminum foil).
  • a current collector such as copper foil and aluminum foil.
  • a pole piece is formed on the upper part and finally assembled into a complete battery core.
  • the existing commercial conductive agents are mostly in the form of micrometers or even nanometer particles, and are not easily dispersed during the stirring process of the slurry. Therefore, it is often necessary to add an excessive amount of conductive agent in practice; this not only reduces the energy density of the battery core, but also excessive conductive agent. It also significantly reduces the first efficiency of the cell.
  • the industry's solution involves the use of a polymer compound having a carboxyl group, a hydroxyl group, and the like, which can be bonded to the silicon surface of the silicon surface as a binder, which is coated on the surface of the silicon particles to bind the powdered crack of the individual silicon particles.
  • a polymer compound having a carboxyl group, a hydroxyl group, and the like which can be bonded to the silicon surface of the silicon surface as a binder, which is coated on the surface of the silicon particles to bind the powdered crack of the individual silicon particles.
  • a conductive agent such as carbon black
  • the binder molecule is small in size (nanoscale), it lacks micron-scale rigid support, and thus Under the action of large volumetric stress caused by the expansion of silicon particles, the nano-sized binder molecules can not bind the micron-sized silicon particles as a whole. Therefore, the binder will lose the bonding effect after the silicon anode is pulverized, eventually leading to electricity. The cycle performance
  • the first aspect of the present invention provides a conductive adhesive for a lithium ion battery, which has good electrical conductivity and bonding performance, and has a certain strength, so as to solve the problem that the existing lithium ion battery needs to be used at the same time.
  • the bonding agent and the conductive agent cause the internal resistance of the cell to increase, the energy density of the cell and the first efficiency decrease; and the existing binder molecules cannot bind the micron-sized silicon particles as a whole, thereby causing the silicon negative electrode.
  • the failure of the binder after pulverization eventually leads to the problem that the cycle performance of the cell is rapidly attenuated.
  • the present invention provides a conductive binder for a lithium ion battery, comprising graphene and a first binder grafted on the surface of the graphene, the first binder comprising polyvinyl alcohol ( PVA), carboxymethyl cellulose (CMC), polyethylene glycol (PEG), polylactic acid (PLA), polymethyl methacrylate (PMMA), polystyrene (PS), polyvinylidene fluoride (PVdF) At least one of a hexafluoropropylene polymer, styrene-butadiene rubber (SBR), sodium alginate, starch, cyclodextrin, and polysaccharide.
  • PVA polyvinyl alcohol
  • CMC carboxymethyl cellulose
  • PEG polyethylene glycol
  • PMMA polylactic acid
  • PMMA polymethyl methacrylate
  • PS polystyrene
  • PVdF polyvinylidene fluoride
  • SBR styrene-butadiene
  • the first binder is at least one of polyvinyl alcohol, sodium carboxymethyl cellulose, polyethylene glycol, sodium alginate, starch, cyclodextrin, and polysaccharide.
  • Lithium ion battery Further comprising a second binder grafted onto the surface of the graphene with a conductive binder, the second binder being coupled to the first binder by a chemical bond, the second binder being a polymer At least one of acrylic acid (PAA) and polyimide (PI).
  • PAA acrylic acid
  • PI polyimide
  • the carboxyl groups in the first binder and the second binder are alkali metal carboxyl groups.
  • the graphene particles have a thickness of 0.35 to 50 nm and a D50 particle diameter of 50 to 5000 nm.
  • the graphene accounts for 0.1 to 10% of the total mass of the conductive binder for the lithium ion battery.
  • the first binder accounts for 20-50% of the total mass of the first binder and the second binder.
  • the conductive adhesive for a lithium ion battery provided by the first aspect of the present invention has good electrical conductivity and bonding property and has a certain strength, so that the conductive adhesive can not only improve the conductivity of the electrode pole piece, Moreover, at a low addition amount, a better combination with an active material (for example, lithium cobaltate, graphite, silicon, etc.) can be achieved, the internal resistance of the cell can be greatly reduced, and the powdering of the active material can be effectively suppressed;
  • the conductive adhesive realizes the combination of the binder and the conductive agent, thereby increasing the content of the active material of the pole piece and further increasing the energy density of the battery core.
  • the present invention provides a method for preparing the above-mentioned conductive adhesive for a lithium ion battery, comprising the following steps:
  • the first binder comprises polyvinyl alcohol, carboxymethyl cellulose, polyethylene glycol, polylactic acid, polymethyl methacrylate, polystyrene, polyvinylidene fluoride, hexafluoropropylene polymer, styrene At least one of butadiene rubber, sodium alginate, starch, cyclodextrin, and polysaccharide.
  • the first binder is at least one of polyvinyl alcohol, sodium carboxymethyl cellulose, polyethylene glycol, sodium alginate, starch, cyclodextrin, and polysaccharide. Further, after the obtaining the first binder graft-modified graphene, taking the monomer of the second binder, and under the action of the initiator, making the second binder single In-situ polymerization is grafted onto the first binder graft-modified graphene, and the second binder is connected to the first binder through a chemical bond to obtain conductive electricity for the lithium ion battery a binder; the second binder is at least one of polyacrylic acid and polyimide.
  • the initiator is selected from the group consisting of ammonium persulfate, alkali metal persulfate, azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), azobisisobutyl hydrazine.
  • AIBN azobisisobutyronitrile
  • BPO benzoyl peroxide
  • azobisisobutyl hydrazine At least one of hydrochloride (AIBA), azobiscyanovaleric acid (ACVA), and azodiisopropylimidazoline (AIP).
  • the first binder comprises polylactic acid
  • the second binder comprises polyacrylic acid
  • the method for preparing a conductive adhesive for a lithium ion battery provided by the second aspect of the present invention has a simple and feasible process and low cost.
  • the present invention provides a lithium ion battery electrode pole piece, comprising a current collector, and an electrode active material coated on the current collector and the conductive paste for the lithium ion battery according to the first aspect of the invention.
  • the conductive binder for the lithium ion battery accounts for 0.5-10% of the total mass of the electrode active material and the conductive binder for the lithium ion battery.
  • the electrode plate of the lithium ion battery provided by the third aspect of the invention has good electrical conductivity, has strong mechanical properties, and has high active material content, and has strong adhesion on the surface of the current collector.
  • the present invention provides a method for preparing a lithium ion battery electrode pole piece, comprising the following steps:
  • the electrode active material and the conductive binder for a lithium ion battery according to the above first aspect of the invention are added to a solvent, uniformly mixed to obtain a slurry, and the slurry is applied to the current collector. On the top, it is dried at 90-120 ° C and then pressed to obtain a lithium ion battery electrode pole piece.
  • the present invention provides a lithium ion battery comprising the conductive adhesive for a lithium ion battery according to the above first aspect of the present invention.
  • the lithium ion battery has high energy density and good cycle performance.
  • FIG. 1 is a schematic structural view of a conductive adhesive for a lithium ion battery according to an embodiment of the present invention
  • FIG. 2 is a schematic structural view of a conductive adhesive for a lithium ion battery according to another embodiment of the present invention.
  • FIG. 3 is a schematic view showing the effect of suppressing the pulverization expansion of silicon particles by a conductive adhesive for a lithium ion battery according to an embodiment of the present invention
  • FIG. 4 is a flow chart showing the synthesis of a conductive adhesive for a lithium ion battery according to Embodiment 1 of the present invention.
  • the silicone-bonded polymer compound acts as a binder and coats the surface of the silicon particles to bind the powdered fragments of the individual silicon particles.
  • the effect is not very satisfactory, because such binders are small in size (nanoscale) and can only bind to the pulverization of the surface of the silicon particles in the microscopic range, but between the macroscopic micron-sized silicon particles and between the silicon particles.
  • the pulverization detachment does not contribute significantly, so the expansion pulverization of silicon or tin alloy cannot be well suppressed.
  • the embodiments of the present invention provide a conductive adhesive for a lithium ion battery, which has good electrical conductivity and bonding properties and has a certain strength.
  • an embodiment of the present invention provides a conductive adhesive for a lithium ion battery, comprising graphene and a first binder grafted on the surface of the graphene, the first binder comprising polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), polyethylene glycol (PEG), polylactic acid (PLA), polymethyl methacrylate (PMMA), polystyrene (PS), polyvinylidene fluoride (PVdF) And at least one of a hexafluoropropylene polymer, styrene-butadiene rubber (SBR), sodium alginate, starch, cyclodextrin, and polysaccharide.
  • PVA polyvinyl alcohol
  • CMC carboxymethyl cellulose
  • PEG polyethylene glycol
  • PMMA polylactic acid
  • PMMA polymethyl methacrylate
  • PS polystyrene
  • PVdF polyvinylidene fluoride
  • SBR styrene-but
  • the hexafluoropropylene polymer includes polyvinylidene fluoride-hexafluoropropylene, hexafluoropropylene dimer, and hexafluoropropylene polymer.
  • Fig. 1 is a schematic view showing the structure of a conductive adhesive for a lithium ion battery in the embodiment. As shown in Fig. 1, the black portion on the left side of the figure is a graphene-based body, and B1 is a polymer segment of the first binder.
  • the conductive adhesive for a lithium ion battery provided by the embodiment of the present invention enhances the mechanical strength of the electrode piece while improving the conductivity of the electrode piece by introducing a graphene skeleton; and grafting the polymer bond on the surface of the graphene
  • the agent can achieve a better combination with an active material (such as lithium cobaltate, graphite, silicon, etc.) at a low conductive binder addition amount.
  • the first binder is polyvinyl alcohol, sodium carboxymethyl cellulose
  • the conductive binder for a lithium ion battery further comprising a second bond grafted on the surface of the graphene when at least one of polyethylene glycol, sodium alginate, starch, cyclodextrin, and polysaccharide
  • the second binder is connected to the first binder by a chemical bond, and the second binder is at least one of polyacrylic acid (PAA) and polyimide (PI).
  • PAA polyacrylic acid
  • PI polyimide
  • the second binder can further effectively suppress expansion of the active material such as silicon particles.
  • 2 is a schematic view showing the structure of a conductive adhesive for a lithium ion battery in the embodiment. As shown in FIG. 2, the black portion on the left side of the figure is a graphene-based body, B1 is a polymer segment of the first binder, and B1 is a polymer segment of the second binder.
  • the carboxyl groups in the first binder and the second binder are alkali metal carboxyl groups. After the carboxyl groups in the first binder and the second binder are neutralized to form a carboxylate, the acidity is lost, thereby avoiding subsequent reaction with lithium hexafluorophosphate in the electrolyte when it is used in a lithium ion battery.
  • the graphene particles have a thickness of 0.35-50 nm and a D50 particle size of 50-5000 nm. In a preferred embodiment of the present invention, the graphene particles have a thickness of 5 nm and a D50 particle diameter of 100 nm.
  • the graphene may be conventional graphene or doped graphene, and the doping element in the doped graphene may include N, B, P, S, F, Cl, O. At least one of them.
  • the graphene may be a single layer of graphene or a multilayer graphene.
  • the graphene accounts for 0.1-10%, preferably 0.5-10%, of the total mass of the conductive binder for the lithium ion battery.
  • the first binder accounts for the first binder and the second binder. 20-50% of the total mass.
  • FIG. 3 1 is silicon particles and 2 is graphene. 3 is a binder molecular chain grafted on graphene.
  • the silicon particles are confined in a hollow space structure constructed by a graphene sheet layer; hydrogen bonds formed between functional groups such as a hydroxyl group and a carboxyl group on the binder polymer chain grafted on the surface of the graphene sheet are A strong bond is formed between adjacent graphene sheets; thus, when the silicon particles are greatly expanded, the graphene sheets around the silicon particles are not completely separated from each other.
  • the polymer chain of the binder When the silicon particles are expanded by lithium, the polymer chain of the binder is stretched to provide a stress release space for volume expansion; when the silicon particles are delithiated and contracted, the binder polymer chain is again entangled and contracted, so that the graphene and the silicon are always in contact. .
  • the binder polymer chain is always covered on the surface of the silicon particles, so that the surface layer of the silicon particles is not detached from the main body after being pulverized, and finally the effective suppression of the pulverization expansion of the silicon particles is achieved.
  • the conductive adhesive for a lithium ion battery provided by the first aspect of the present invention has good electrical conductivity and bonding property and has a certain strength, so that the conductive adhesive can not only improve the conductivity of the electrode pole piece, Moreover, at a low addition amount, a better combination with an active material (for example, lithium cobaltate, graphite, silicon, etc.) can be achieved, the internal resistance of the cell can be greatly reduced, and the powdering of the electrode active material can be effectively suppressed;
  • the conductive adhesive realizes the combination of the binder and the conductive agent, thereby increasing the content of the active material of the pole piece and further increasing the energy density of the battery core.
  • the conductive adhesive for lithium ion batteries provided by the embodiments of the present invention can be used for a negative electrode of a lithium ion battery, and can also be used for a positive electrode. Applying the conductive adhesive for lithium ion batteries provided by the embodiments of the present invention to a conventional graphite negative electrode or positive electrode can enhance the electrical conductivity of the electrode and the bonding performance of the particles, reduce the internal resistance of the battery, and improve the rate performance and cycle performance of the battery.
  • the graphene skeleton in the conductive binder When applied to a negative electrode of silicon, tin or alloy, the graphene skeleton in the conductive binder also acts as a binder to provide a rigid support for the binder, thereby limiting the protective effect of the expansion and pulverization of the anode, and finally effectively improving the silicon, Cyclic stability of tin or alloy negative electrodes.
  • an embodiment of the present invention provides a method for preparing the above conductive adhesive for a lithium ion battery, comprising the following steps:
  • the first binder is grafted to the surface of the graphene oxide; or the monomer of the first binder is polymerized and grafted to the monomer of the first binder by atom transfer radical polymerization
  • the surface of the graphene oxide is obtained by graft-modifying the first binder to obtain the conductive binder for the lithium ion battery; the first binder comprises polyvinyl alcohol and carboxymethyl fiber.
  • polyethylene glycol polylactic acid, polymethyl methacrylate, polystyrene, polyvinylidene fluoride, hexafluoropropylene polymer, styrene-butadiene rubber, sodium alginate, starch, cyclodextrin and At least one of the polysaccharides.
  • the first binder is taken, and the first binder is grafted to the surface of the graphene oxide by a condensation reaction.
  • the method is suitable for the grafting of polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), polyethylene glycol (PEG), sodium alginate, starch, cyclodextrin and polysaccharides.
  • the monomer of the first binder is polymerized and grafted onto the surface of the graphene oxide by atom transfer radical polymerization.
  • the method is applicable to polylactic acid (PLA), polymethyl methacrylate (PMMA), polystyrene (PS), polyvinylidene fluoride (PVdF), hexafluoropropylene polymer (HFP), styrene-butadiene. Grafting of rubber (SBR).
  • the monomer of the second binder includes lactic acid, methyl methacrylate, styrene, vinylidene fluoride, hexafluoropropylene, butadiene.
  • the specific reaction conditions required for the condensation reaction and the atom transfer radical polymerization reaction including the solvent required for the reaction, the reaction temperature, the reaction time, etc., may be determined according to the specific type of the first binder to be grafted.
  • the invention is not particularly limited.
  • the specific operation of the oxidation treatment is: heating the graphene to a graphene oxide in an aqueous solution or atmosphere of a strong oxidant to 50-95 ° C; the strong oxidizing agent is selected from the group consisting of sulfuric acid, nitric acid, and perchloric acid. And at least one of ammonium persulfate, alkali metal persulfate, alkali metal permanganate, alkali metal dichromate, hydrogen peroxide, and ozone.
  • the graphene oxide surface has a large amount of carboxyl functional groups.
  • the first binder is at least one of polyvinyl alcohol, sodium carboxymethyl cellulose, polyethylene glycol, sodium alginate, starch, cyclodextrin, and polysaccharide Further included in getting After the first binder is graft-modified graphene, the monomer of the second binder is taken, and the monomer of the second binder is polymerized in situ by the action of the initiator. On the first binder graft-modified graphene, the second binder is connected to the first binder through a chemical bond to obtain the conductive binder for the lithium ion battery; The second binder is at least one of polyacrylic acid and polyimide.
  • the initiator is selected from the group consisting of ammonium persulfate, alkali metal persulfate, azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), azobisisobutylphosphonium hydrochloride At least one of a salt (AIBA), azobiscyanovaleric acid (ACVA), and azodiisopropylimidazoline (AIP). If the initiator selects persulfate, it is supplemented with sodium bisulfite, and the mass ratio of persulfate to sodium bisulfite is 100:1-1:1.
  • the first binder comprises polylactic acid
  • the second binder comprises polyacrylic acid
  • the carboxyl group in the process is alkali metallized.
  • the aqueous alkali metal hydroxide solution may be lithium hydroxide, sodium hydroxide or potassium hydroxide.
  • the pH of the system is neutralized to 6-7 with an aqueous alkali metal hydroxide solution to form a carboxylate.
  • the preparation method of the conductive adhesive for a lithium ion battery provided by the embodiment of the invention is simple and feasible, and the cost is low.
  • an embodiment of the present invention further provides a lithium ion battery electrode pole piece, comprising a current collector, and an electrode active material coated on the current collector, and the conductive adhesive for a lithium ion battery according to the embodiment of the invention.
  • the conductive binder for the lithium ion battery accounts for 0.5-10%, preferably 2-5%, of the total mass of the electrode active material and the conductive binder for the lithium ion battery.
  • the electrode sheet of the lithium ion battery provided by the embodiment of the invention has good electrical conductivity, has strong mechanical properties, and has high active substance content, and has strong adhesion on the surface of the current collector.
  • an embodiment of the present invention further provides a method for preparing a lithium ion battery electrode pole piece, including The following steps:
  • the conductive binder for the lithium ion battery accounts for 0.5-10%, preferably 2-5%, of the total mass of the electrode active material and the conductive binder for the lithium ion battery.
  • the lithium ion battery electrode tab can be pressed to a desired thickness, which may be 0.05-0.15 mm.
  • the solvent includes water, N-methylpyrrolidone (NMP), and the like.
  • an embodiment of the present invention provides a lithium ion battery comprising the above-described conductive adhesive for a lithium ion battery according to an embodiment of the present invention.
  • the lithium ion battery has high energy density and good cycle performance.
  • a method for preparing a conductive adhesive for a lithium ion battery comprising the steps of:
  • the product can be used as a conductive agent and a binder in the preparation of a slurry of a lithium ion battery graphite, silicon, an alloy thereof, or the like.
  • G-PVA-b-PAALi with different values of a, b, and n can be obtained by changing the material ratio.
  • the value of a ranges from 50 to 100,000, and the value of b ranges from 50 to 100,000. It is 100-200000.
  • a ranges from 500 to 20,000, b ranges from 500 to 20,000, and n ranges from 1000 to 20,000.
  • the silicon negative electrode material (particle size: 100 nm) and the conductive binder G-PVA-b-PAALi for lithium ion battery prepared in this example are uniformly mixed in water at a mass ratio of 93:7 to obtain a negative electrode slurry.
  • the obtained negative electrode slurry was coated on a copper foil current collector and dried under vacuum at 110 ° C to obtain a negative electrode sheet, which was then assembled into a button cell in a glove box for testing.
  • the counter electrode was made of lithium metal and the diaphragm was celgard. C2400, the electrolyte was a solution of 1.3 M LiPF 6 in EC, PC and DEC (3:1:6 by volume).
  • a method for preparing a conductive adhesive for a lithium ion battery comprising the steps of:
  • the product can be used as a conductive agent and a binder in the preparation of a lithium ion battery positive electrode material and a graphite negative electrode material.
  • lithium cobaltate and the conductive binder G-PVdF powder for lithium ion battery prepared in this example were mixed in a mass ratio of 93:7 in N-methylpyrrolidone (NMP) to obtain a positive electrode.
  • NMP N-methylpyrrolidone
  • the slurry was applied to an aluminum foil current collector and vacuum dried at 120 ° C to obtain a positive electrode sheet, which was then assembled into a button cell in a glove box for testing.
  • the counter electrode was made of lithium metal and the diaphragm was celgard. C2400, the electrolyte was a solution of 1.3 M LiPF 6 in EC, PC and DEC (3:1:6 by volume).
  • a method for preparing a conductive adhesive for a lithium ion battery comprising the steps of:
  • the product can be used in the preparation of a slurry of a lithium ion battery graphite, silicon and its alloys, etc. Used as a conductive agent and a binder.
  • the silicon negative electrode material (particle size: 100 nm) and the conductive binder G-PVA-b-PAALi for lithium ion battery prepared in this example are uniformly mixed in water at a mass ratio of 93:7 to obtain a negative electrode slurry.
  • the obtained negative electrode slurry was coated on a copper foil current collector and dried under vacuum at 110 ° C to obtain a negative electrode sheet, which was then assembled into a button cell in a glove box for testing.
  • the counter electrode was made of lithium metal and the diaphragm was celgard. C2400, the electrolyte was a solution of 1.3 M LiPF 6 in EC, PC and DEC (3:1:6 by volume).
  • a method for preparing a conductive adhesive for a lithium ion battery comprising the steps of:
  • the product can be used as a conductive agent and a binder in the preparation of a slurry of a lithium ion battery graphite, silicon, an alloy thereof, or the like.
  • the silicon negative electrode material (particle size: 100 nm) and the conductive binder G-PVA-b-PAALi for lithium ion battery prepared in this example are uniformly mixed in water at a mass ratio of 93:7 to obtain a negative electrode slurry.
  • the obtained negative electrode slurry was coated on a copper foil current collector and dried under vacuum at 110 ° C to obtain a negative electrode sheet, which was then assembled into a button cell in a glove box for testing.
  • the counter electrode was made of lithium metal and the diaphragm was celgard. C2400, the electrolyte was a solution of 1.3 M LiPF 6 in EC, PC and DEC (3:1:6 by volume).
  • the first embodiment of the button cell is charged with a current of 100 mA / 1 g of active material to a voltage of 0.001 V, followed by a constant voltage until the current is less than 10 mA / 1 g of active substance; for 10 mins; and the above button cell is 100 mA / 1 g
  • the current of the active material was discharged to 2.5V.
  • the completion of the above charging and discharging process is recorded as one charging/discharging cycle.
  • the first charge and discharge capacity of the battery and the charge and discharge capacity of 50 cycles of charge and discharge were recorded.
  • the second embodiment of the button cell is charged with a current of 100 mA / 1 g of active material to a voltage of 4.4 V, followed by a constant voltage until the current is less than 10 mA / 1 g of active substance; for 10 mins; and the above button cell is 100 mA / 1 g
  • the current of the active material was discharged to 3.0V.
  • the completion of the above charging and discharging process is recorded as one charging/discharging cycle.
  • the first charge and discharge capacity of the battery and the charge and discharge capacity of 50 cycles of charge and discharge were recorded.
  • Capacity retention rate (%) of the nth cycle discharge capacity of the nth cycle / release of the 1st cycle Capacity ⁇ 100%.
  • the conductive adhesive for lithium ion battery prepared by the embodiment of the invention can effectively buffer the negative influence caused by the volume change of the active material during the charging and discharging process, improve the cycle characteristics of the battery, and conduct electricity for the lithium ion battery.
  • the binder acts as both a conductive agent and a binder, and can increase the content of the active material of the positive and negative electrodes, thereby increasing the energy density of the cell.

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Abstract

本发明提供了一种锂离子电池用导电粘结剂，包括石墨烯以及接枝在所述石墨烯表面的第一粘结剂，所述第一粘结剂包括聚乙烯醇、羧甲基纤维素钠、聚乙二醇、聚乳酸、聚甲基丙烯酸甲酯、聚苯乙烯、聚偏氟乙烯、六氟丙烯聚合物、苯乙烯-丁二烯橡胶、海藻酸钠、淀粉、环糊精和多聚糖中的至少一种。该锂离子电池用导电粘结剂兼具良好的导电性能和粘结性能，且具有一定的强度可增强电极极片整体的力学强度，该导电粘结剂实现了粘结剂与导电剂合二为一，因此可提高极片活性物质的含量，进一步提升电芯能量密度。本发明还提供了该导电粘结剂的制备方法，以及包含该导电粘结剂的电极极片和锂离子电池。

Description

一种锂离子电池用导电粘结剂及其制备方法、锂离子电池电极极片及制备方法和锂离子电池
本申请要求了2016年5月12日提交中国专利局的，申请号201610318938.7，发明名称为“一种锂离子电池用导电粘结剂及其制备方法、锂离子电池电极极片及制备方法和锂离子电池”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及锂离子电池领域，特别是涉及一种锂离子电池用导电粘结剂及其制备方法、锂离子电池电极极片及其制备方法和锂离子电池。
背景技术
锂离子电池由于具有能量密度较高、循环寿命长、免维护等优点，目前已广泛应用于便携式电子设备、电动汽车、储能电器等领域。
现有锂离子电池制备工艺，是将活性物质(正极或负极活性材料)粉末，与导电剂及粘结剂在溶剂中分散成浆料后，再涂布在集流体(如铜箔和铝箔)上形成极片，最后组装成完整的电芯。然而现有商品化导电剂多以微米甚至纳米颗粒形式存在，在浆料搅拌过程中不易分散，因此实践中往往需要加入过量的导电剂；这不仅降低了电芯能量密度，且过量的导电剂还会显著降低电芯的首次效率。而为使导电剂在溶剂中尽量分散，也需要向浆料中加入足量的粘结剂/分散剂，这样又会降低该浆料制备的极片的导电性，增大电芯内阻。
此外，随着手机等便携式电子设备的功耗逐年增大，市场对高能量密度锂离子电池的需求也越来越迫切。而显著提升锂离子电池能量密度的技术方案之一， 就是将现有的石墨负极材料替换为硅等合金材料。然而，硅材料在循环过程中会发生显著的体积膨胀(>300％)，造成硅颗粒的粉化并从集流体脱落，从而导致电芯的循环性能迅速衰减。目前业内的解决方案包括采用带有羧基、羟基等能与硅表面的硅氧键结合的高分子化合物做粘结剂，包覆在硅颗粒表面，束缚单个硅颗粒的粉化碎裂。然而，现有解决方案仅是对传统粘结剂的改善，仍需加入炭黑等导电剂；此外，粘结剂分子由于尺寸较小(纳米级)，其缺乏微米尺度的刚性支撑，因此在硅颗粒体积膨胀产生巨大应力的作用下，纳米尺寸的粘结剂分子无法束缚微米尺度的硅颗粒整体的粉化碎裂，因此硅负极粉化后粘结剂将失去粘结效果，最终导致电芯的循环性能迅速衰减。
发明内容
鉴于此，本发明第一方面提供了一种锂离子电池用导电粘结剂，其兼具良好的导电性能和粘结性能，且具有一定的强度，以解决现有锂离子电池需同时使用粘结剂和导电剂，导致电芯内阻增大，电芯能量密度和首次效率降低的问题；以及现有粘结剂分子无法束缚微米尺度的硅颗粒整体的粉化碎裂，从而导致硅负极粉化后粘结剂失效，最终导致电芯的循环性能迅速衰减的问题。
第一方面，本发明提供了一种锂离子电池用导电粘结剂，包括石墨烯以及接枝在所述石墨烯表面的第一粘结剂，所述第一粘结剂包括聚乙烯醇(PVA)、羧甲基纤维素(CMC)、聚乙二醇(PEG)、聚乳酸(PLA)、聚甲基丙烯酸甲酯(PMMA)、聚苯乙烯(PS)、聚偏氟乙烯(PVdF)、六氟丙烯聚合物、苯乙烯-丁二烯橡胶(SBR)、海藻酸钠、淀粉、环糊精和多聚糖中的至少一种。
在本发明第一方面中，当所述第一粘结剂为聚乙烯醇、羧甲基纤维素钠、聚乙二醇、海藻酸钠、淀粉、环糊精和多聚糖中的至少一种时，所述锂离子电池 用导电粘结剂进一步包括接枝在所述石墨烯表面的第二粘结剂，所述第二粘结剂通过化学键与所述第一粘结剂连接，所述第二粘结剂为聚丙烯酸(PAA)和聚酰亚胺(PI)中的至少一种。
在本发明第一方面中，所述第一粘结剂和所述第二粘结剂中的羧基均为碱金属化羧基。
在本发明第一方面中，所述石墨烯粒子厚度为0.35-50nm，D50粒径为50-5000nm。
在本发明第一方面中，所述石墨烯占所述锂离子电池用导电粘结剂总质量的0.1-10％。
在本发明第一方面中，所述第一粘结剂占所述第一粘结剂和所述第二粘结剂总质量的20-50％。
本发明第一方面提供的一种锂离子电池用导电粘结剂，兼具良好的导电性能和粘结性能，且具有一定的强度，因此该导电粘结剂不但能提高电极极片导电性，而且在低添加量下，能实现更好的与活性物质(例如钴酸锂、石墨、硅等)结合的效果，可大大降低电芯内阻，并能有效抑制活性物质的粉化；此外，该导电粘结剂实现粘结剂与导电剂合二为一，从而可提高极片活性物质的含量，进一步提升电芯能量密度。
第二方面，本发明提供了一种上述的锂离子电池用导电粘结剂的制备方法，包括以下步骤：
取石墨烯进行氧化处理后得到氧化石墨烯；取第一粘结剂，通过缩合反应使所述第一粘结剂接枝到所述氧化石墨烯表面；或取第一粘结剂的单体，通过原子转移自由基聚合反应使所述第一粘结剂的单体聚合接枝到所述氧化石墨烯表面，得到第一粘结剂接枝改性的石墨烯，即得到所述锂离子电池用导电粘结剂； 所述第一粘结剂包括聚乙烯醇、羧甲基纤维素、聚乙二醇、聚乳酸、聚甲基丙烯酸甲酯、聚苯乙烯、聚偏氟乙烯、六氟丙烯聚合物、苯乙烯-丁二烯橡胶、海藻酸钠、淀粉、环糊精和多聚糖中的至少一种。
在本发明第二方面中，当所述第一粘结剂为聚乙烯醇、羧甲基纤维素钠、聚乙二醇、海藻酸钠、淀粉、环糊精和多聚糖中的至少一种时，进一步包括在得到所述第一粘结剂接枝改性的石墨烯后，取第二粘结剂的单体，在引发剂的作用下，使所述第二粘结剂的单体原位聚合接枝到所述第一粘结剂接枝改性的石墨烯上，所述第二粘结剂通过化学键与所述第一粘结剂连接，得到所述锂离子电池用导电粘结剂；所述第二粘结剂为聚丙烯酸和聚酰亚胺中的至少一种。
在本发明第二方面中，所述引发剂选自过硫酸铵、过硫酸碱金属盐、偶氮二异丁腈(AIBN)、过氧化苯甲酰(BPO)、偶氮二异丁基脒盐酸盐(AIBA)、偶氮二氰基戊酸(ACVA)、偶氮二异丙基咪唑啉(AIP)中的至少一种。
在本发明第二方面中，当所述第一粘结剂包括聚乳酸时，或当所述第二粘结剂包括聚丙烯酸时，进一步包括采用碱金属氢氧化物水溶液将所述聚乳酸或聚丙烯酸中的羧基进行碱金属化处理。
本发明第二方面提供的锂离子电池用导电粘结剂的制备方法，工艺简单可行，成本低廉。
第三方面，本发明提供了一种锂离子电池电极极片，包括集流体，以及涂覆在所述集流体上的电极活性材料和本发明上述第一方面所述的锂离子电池用导电粘结剂。该锂离子电池电极极片中，所述锂离子电池用导电粘结剂占所述电极活性材料与所述锂离子电池用导电粘结剂总质量的0.5-10％。
本发明第三方面提供的锂离子电池电极极片具有良好的导电性，同时具有较强的力学性能，且活性物质含量较高，在集流体表面粘结力强。
第四方面，本发明提供了一种锂离子电池电极极片的制备方法，包括以下步骤：
取集流体，将电极活性材料和本发明上述第一方面所述的锂离子电池用导电粘结剂加入到溶剂中，混合均匀，得到浆料，将所述浆料涂敷在所述集流体上，于90-120℃烘干后压制，得到锂离子电池电极极片。
第五方面，本发明提供了一种锂离子电池，其包含本发明上述第一方面所述的锂离子电池用导电粘结剂。该锂离子电池具有较高的能量密度和良好的循环性能。
本发明的优点将会在下面的说明书中部分阐明，一部分根据说明书是显而易见的，或者可以通过本发明实施例的实施而获知。
附图说明
图1为本发明一实施方式中锂离子电池用导电粘结剂的结构示意图；
图2为本发明另一实施方式中锂离子电池用导电粘结剂的结构示意图；
图3为本发明实施例锂离子电池用导电粘结剂抑制硅颗粒粉化膨胀的效果示意图；
图4为本发明实施例一中锂离子电池用导电粘结剂的合成流程图。
具体实施方式
以下所述是本发明实施例的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明实施例原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本发明实施例的保护范围。
目前，在锂离子电池制备工艺中，为了获得性能良好的电极极片，通常需要 在制备浆料时同时加入粘结剂和导电剂，然而这些组分的加入会导致电芯内阻增大，电芯能量密度和首次效率降低；且对于现有以硅或锡合金为负极的电池，其在循环过程中，硅或锡合金的膨胀粉化现象严重，因此导致电芯的循环性能衰减严重，为了解决这一问题，业内试图通过采用带有羧基、羟基等能与硅表面的硅氧键结合的高分子化合物做粘结剂，包覆在硅颗粒表面，束缚单个硅颗粒的粉化碎裂。然而，效果并不十分理想，因为这类粘结剂分子尺寸较小(纳米级)，仅能束缚微观范围内硅颗粒表面的粉化，而对宏观微米级硅颗粒内部及硅颗粒之间的粉化脱离无明显帮助，因此无法很好地抑制硅或锡合金的膨胀粉化。为了一并解决上述的问题，本发明实施例提供了一种锂离子电池用导电粘结剂，其兼具良好的导电性能和粘结性能，且具有一定的强度。
具体地，本发明实施例提供了一种锂离子电池用导电粘结剂，包括石墨烯以及接枝在所述石墨烯表面的第一粘结剂，所述第一粘结剂包括聚乙烯醇(PVA)、羧甲基纤维素(CMC)、聚乙二醇(PEG)、聚乳酸(PLA)、聚甲基丙烯酸甲酯(PMMA)、聚苯乙烯(PS)、聚偏氟乙烯(PVdF)、六氟丙烯聚合物、苯乙烯-丁二烯橡胶(SBR)、海藻酸钠、淀粉、环糊精和多聚糖中的至少一种。其中，六氟丙烯聚合物包括聚偏氟乙烯-六氟丙烯、六氟丙烯二聚体、六氟丙烯多聚体。图1为本实施方式中锂离子电池用导电粘结剂的结构示意图。如图1所示，图中左侧黑色部分为石墨烯基体，B1为第一粘结剂的高分子链段。
本发明实施例提供的锂离子电池用导电粘结剂通过引入石墨烯骨架，在提高电极极片导电性的同时，增强了极片整体的力学强度；而在石墨烯表面接枝高分子粘结剂，可以在低导电粘结剂添加量下，实现更好的与活性物质(例如钴酸锂、石墨、硅等)结合的效果。
本发明另一实施方式中，当所述第一粘结剂为聚乙烯醇、羧甲基纤维素钠、 聚乙二醇、海藻酸钠、淀粉、环糊精和多聚糖中的至少一种时，所述锂离子电池用导电粘结剂进一步包括接枝在所述石墨烯表面的第二粘结剂，所述第二粘结剂通过化学键与所述第一粘结剂连接，所述第二粘结剂为聚丙烯酸(PAA)和聚酰亚胺(PI)中的至少一种。所述第二粘结剂可进一步有效抑制硅颗粒等活性材料的膨胀。图2为本实施方式中锂离子电池用导电粘结剂的结构示意图。如图2所示，图中左侧黑色部分为石墨烯基体，B1为第一粘结剂的高分子链段，B2第二粘结剂的高分子链段。
本发明实施方式中，所述第一粘结剂和所述第二粘结剂中的羧基均为碱金属化羧基。第一粘结剂和第二粘结剂中的羧基被中和形成羧酸盐后，失去酸性，从而避免了后续其在锂离子电池中使用时与电解液中的六氟磷酸锂发生反应。
本发明实施方式中，所述石墨烯粒子厚度为0.35-50nm，D50粒径为50-5000nm。本发明一优选实施方式中，所述石墨烯粒子厚度为5nm，D50粒径为100nm。通过选择合适尺寸大小的石墨烯，不但有利于分散，提供良好的导电性，还可以使导电粘结剂获得一定强度。
本发明实施方式中，所述石墨烯可以是常规的石墨烯，也可以是掺杂石墨烯，掺杂石墨烯中的掺杂元素可包括N、B、P、S、F、Cl、O中的至少一种。所述石墨烯可以是单层石墨烯，也可以是多层石墨烯。
本发明实施方式中，所述石墨烯占所述锂离子电池用导电粘结剂总质量的0.1-10％，优选为0.5-10％。
本发明实施方式中，当石墨烯表面同时接枝有第一粘结剂和第二粘结剂时，所述第一粘结剂占所述第一粘结剂和所述第二粘结剂总质量的20-50％。
为了更清楚地说明本发明实施例所述锂离子电池用导电粘结剂抑制硅颗粒粉化膨胀的效果，请参见图3的效果示意图。图3中，1为硅颗粒，2为石墨烯， 3为接枝在石墨烯上的粘结剂分子链。如图3所示，硅颗粒被限制在由石墨烯片层搭建的中空空间结构内；石墨烯片表面接枝的粘结剂高分子链上的羟基、羧基等官能团间形成的氢键，在相邻石墨烯片之间形成强有力的结合；这样当硅颗粒大幅膨胀时，硅颗粒周围的石墨烯片不会彼此完全分离。当硅颗粒嵌锂膨胀时，粘结剂高分子链伸展，为体积膨胀提供应力释放空间；当硅颗粒脱锂收缩时，粘结剂高分子链再次缠绕收缩，使得石墨烯与硅始终保持接触。此外，粘结剂高分子链始终覆盖在硅颗粒表面，使得硅颗粒表面层粉化后不会与主体脱离，最终实现对硅颗粒粉化膨胀的有效抑制。
本发明第一方面提供的一种锂离子电池用导电粘结剂，兼具良好的导电性能和粘结性能，且具有一定的强度，因此该导电粘结剂不但能提高电极极片导电性，而且在低添加量下，能实现更好的与活性物质(例如钴酸锂、石墨、硅等)结合的效果，可大大降低电芯内阻，并能有效抑制电极活性物质的粉化；此外，该导电粘结剂实现粘结剂与导电剂合二为一，从而可提高极片活性物质的含量，进一步提升电芯能量密度。
本发明实施例提供的锂离子电池用导电粘结剂可用于锂离子电池负极，也可以用于正极。将本发明实施例提供的锂离子电池用导电粘结剂应用到传统石墨负极或正极中，可增强电极的导电性能和颗粒的粘结性能，降低电池内阻，提升电池的倍率性能和循环性能；而应用到硅、锡或合金负极时，导电粘结剂中的石墨烯骨架还起到包裹颗粒、为粘结剂提供刚性支撑，从而限制负极膨胀粉化的保护作用，最终有效改善硅、锡或合金负极的循环稳定性。
相应地，本发明实施例提供了一种上述的锂离子电池用导电粘结剂的制备方法，包括以下步骤：
取石墨烯进行氧化处理后得到氧化石墨烯；取第一粘结剂，通过缩合反应使 所述第一粘结剂接枝到所述氧化石墨烯表面；或取第一粘结剂的单体，通过原子转移自由基聚合反应使所述第一粘结剂的单体聚合接枝到所述氧化石墨烯表面，得到第一粘结剂接枝改性的石墨烯，即得到所述锂离子电池用导电粘结剂；所述第一粘结剂包括聚乙烯醇、羧甲基纤维素、聚乙二醇、聚乳酸、聚甲基丙烯酸甲酯、聚苯乙烯、聚偏氟乙烯、六氟丙烯聚合物、苯乙烯-丁二烯橡胶、海藻酸钠、淀粉、环糊精和多聚糖中的至少一种。
具体地，对于方法1：取第一粘结剂，通过缩合反应使所述第一粘结剂接枝到所述氧化石墨烯表面。该方法适用于聚乙烯醇(PVA)、羧甲基纤维素(CMC)、聚乙二醇(PEG)、海藻酸钠、淀粉、环糊精和多聚糖的接枝。
对于方法2：取第一粘结剂的单体，通过原子转移自由基聚合反应使所述第一粘结剂的单体聚合接枝到所述氧化石墨烯表面。该方法适用于聚乳酸(PLA)、聚甲基丙烯酸甲酯(PMMA)、聚苯乙烯(PS)、聚偏氟乙烯(PVdF)、六氟丙烯聚合物(HFP)、苯乙烯-丁二烯橡胶(SBR)的接枝。所述第二粘结剂的单体包括乳酸、甲基丙烯酸甲酯、苯乙烯、偏氟乙烯、六氟丙烯、丁二烯。
本发明实施方式中，上述缩合反应和原子转移自由基聚合反应所需的具体反应条件，包括反应所需溶剂、反应温度、反应时间等可根据具体待接枝的第一粘结剂种类而定，本发明不作特殊限定。
本发明实施方式中，氧化处理的具体操作为：将石墨烯在强氧化剂的水溶液或气氛中，加热到50-95℃，形成氧化石墨烯；所述强氧化剂选自硫酸、硝酸、高氯酸、过硫酸铵盐、过硫酸碱金属盐、高锰酸碱金属盐、重铬酸碱金属盐、双氧水和臭氧中的至少一种。氧化石墨烯表面具有大量的羧基官能团。
本发明实施方式中，当所述第一粘结剂为聚乙烯醇、羧甲基纤维素钠、聚乙二醇、海藻酸钠、淀粉、环糊精和多聚糖中的至少一种时，进一步包括在得到 所述第一粘结剂接枝改性的石墨烯后，取第二粘结剂的单体，在引发剂的作用下，使所述第二粘结剂的单体原位聚合接枝到所述第一粘结剂接枝改性的石墨烯上，所述第二粘结剂通过化学键与所述第一粘结剂连接，得到所述锂离子电池用导电粘结剂；所述第二粘结剂为聚丙烯酸和聚酰亚胺中的至少一种。
本发明实施方式中，所述引发剂选自过硫酸铵、过硫酸碱金属盐、偶氮二异丁腈(AIBN)、过氧化苯甲酰(BPO)、偶氮二异丁基脒盐酸盐(AIBA)、偶氮二氰基戊酸(ACVA)、偶氮二异丙基咪唑啉(AIP)中的至少一种。如果引发剂选择过硫酸盐，则需辅以亚硫酸氢钠，且过硫酸盐与亚硫酸氢钠的质量比为100:1-1:1。
本发明实施方式中，当所述第一粘结剂包括聚乳酸时，或当所述第二粘结剂包括聚丙烯酸时，进一步包括采用碱金属氢氧化物水溶液将所述聚乳酸或聚丙烯酸中的羧基进行碱金属化处理。碱金属氢氧化物水溶液可以是氢氧化锂、氢氧化钠、氢氧化钾。采用碱金属氢氧化物水溶液将体系pH中和至6-7，形成羧酸盐。
本发明实施例提供的锂离子电池用导电粘结剂的制备方法，工艺简单可行，成本低廉。
此外，本发明实施例还提供了一种锂离子电池电极极片，包括集流体，以及涂覆在所述集流体上的电极活性材料和本发明实施例上述的锂离子电池用导电粘结剂。该锂离子电池电极极片中，所述锂离子电池用导电粘结剂占所述电极活性材料与所述锂离子电池用导电粘结剂总质量的0.5-10％，优选为2-5％。
本发明实施例提供的锂离子电池电极极片具有良好的导电性，同时具有较强的力学性能，且活性物质含量较高，在集流体表面粘结力强。
相应地，本发明实施例还提供了一种锂离子电池电极极片的制备方法，包括 以下步骤：
取集流体，将电极活性材料和本发明实施例上述的锂离子电池用导电粘结剂加入到溶剂中，混合均匀，得到浆料，将所述浆料涂敷在所述集流体上，于90-120℃烘干后压制，得到锂离子电池电极极片。
所述锂离子电池用导电粘结剂占所述电极活性材料与所述锂离子电池用导电粘结剂总质量的0.5-10％，优选为2-5％。所述锂离子电池电极极片可压制成所需要的厚度，可以是0.05-0.15mm。所述溶剂包括水、N-甲基吡咯烷酮(NMP)等。
最后，本发明实施例提供了一种锂离子电池，其包含本发明实施例上述的锂离子电池用导电粘结剂。该锂离子电池具有较高的能量密度和良好的循环性能。
下面分多个实施例对本发明实施例进行进一步的说明。其中，本发明实施例不限定于以下的具体实施例。在不变主权利的范围内，可以适当的进行变更实施。
实施例一
一种锂离子电池用导电粘结剂的制备方法，包括以下步骤：
(1)称取10g石墨烯，与100g浓硝酸(65wt％)水溶液混合后，加热至95℃，搅拌4h后，水洗干燥，得到氧化石墨烯样品G；
(2)将10g氧化石墨烯样品G加入到100ml二甲亚砜(DMSO)中，加入2g二氯亚砜，室温下搅拌反应2h，反应完毕用DMSO洗涤后，重新分散于DMSO中，并加入2g PVA，120℃下搅拌2h，水洗后干燥，得到PVA接枝改性的石墨烯G-PVA；
(3)将G-PVA分散于水中，先通入氮气除去氧，然后在搅拌下加入2g丙烯酸、0.1g K2S2O8与0.03g NaHSO3，加热至55℃，反应2-4h，反应完毕，水洗 后干燥，得到聚乙烯醇-聚丙烯酸(PVA-PAA)接枝的石墨烯G-PVA-b-PAA；
(4)将G-PVA-b-PAA分散于水中，加入LiOH水溶液中和至pH～6，水洗后干燥，得到最终产物G-PVA-b-PAALi，即得到锂离子电池用导电粘结剂。
该产物可在锂离子电池石墨、硅及其合金等负极材料的浆料制备过程中，作为导电剂和粘结剂使用。
图4为本实施例的锂离子电池用导电粘结剂的合成流程图。通过改变物料配比等可获得不同a、b、n取值的G-PVA-b-PAALi，a的取值范围为50-100000，b的取值范围为50-100000，n的取值范围为100-200000。优选地，a的取值范围为500-20000，b的取值范围为500-20000，n的取值范围为1000-20000。
锂离子电池的制备：将硅负极材料(粒径100nm)与本实施例制备得到的锂离子电池用导电粘结剂G-PVA-b-PAALi按照质量比93:7在水中混合均匀得到负极浆料，将所得负极浆料涂于铜箔集流体上，110℃真空烘干，得到负极电极片，然后在手套箱中组装成扣式电池进行测试，其中，对电极采用锂金属，隔膜为celgard C2400，电解液为1.3M LiPF6的EC、PC和DEC(体积比为3:1:6)溶液。
实施例二
一种锂离子电池用导电粘结剂的制备方法，包括以下步骤：
(1)称取10g石墨烯，与100g浓硝酸(65wt％)水溶液混合后，加热至95℃，搅拌4h后，水洗干燥，得到氧化石墨烯样品G。
(2)将10g氧化石墨烯搅拌下分散于100ml四氢呋喃(THF)中，加入1g乙硼烷，室温下搅拌12h，将氧化石墨烯表面的羧基、酸酐、羰基等还原为醇羟基；然后用THF洗涤并干燥后，重新分散于2g吡啶与100mL干燥乙醚的混合溶液中，加入2g 2-溴异丁基酰溴(BiBB)，0℃下缓慢搅拌2h，然后再在室 温下搅拌反应10h，经无水乙醇洗涤后干燥，得到羟基溴化的氧化石墨烯G-Br；
(3)将100mL甲醇、3g偏二氟乙烯、0.02g溴化亚铜(CuBr)、0.05g 2,2’-联吡啶(Bpy)加入反应器中，室温下进行氩气鼓泡30min除去体系中的氧；然后在氩气保护气氛下，加入上述G-Br粉末，密闭反应器在室温下搅拌反应24h，反应后过滤，以无水甲醇洗涤干燥，得到聚偏氟乙烯接枝改性的石墨烯样品G-PVdF，即得到锂离子电池用导电粘结剂。
该产物可在锂离子电池正极材料，以及石墨负极材料的浆料制备过程中，作为导电剂和粘结剂使用。
锂离子电池的制备：将钴酸锂与本实施例制备得到的锂离子电池用导电粘结剂G-PVdF粉末，按照质量比93：7在N-甲基吡咯烷酮(NMP)中混合均匀得到正极浆料，将所得正极浆料涂于铝箔集流体上，120℃真空烘干，得到正极电极片，然后在手套箱中组装成扣式电池进行测试，其中，对电极采用锂金属，隔膜为celgard C2400，电解液为1.3M LiPF6的EC、PC和DEC(体积比为3:1:6)溶液。
实施例三
一种锂离子电池用导电粘结剂的制备方法，包括以下步骤：
(1)称取10g石墨烯，与100g浓硝酸(65wt％)水溶液混合后，加热至95℃，搅拌4h后，水洗干燥，得到氧化石墨烯样品G；
(2)将10g氧化石墨烯样品G加入到200ml二甲亚砜(DMSO)中，加入15g二氯亚砜，室温下搅拌反应4h，反应完毕用DMSO洗涤后，重新分散于DMSO中，并加入3g羧甲基纤维素钠，120℃下搅拌6h，水洗后干燥，得到羧甲基纤维素钠接枝改性的石墨烯G-CMC；
该产物可在锂离子电池石墨、硅及其合金等负极材料的浆料制备过程中， 作为导电剂和粘结剂使用。
锂离子电池的制备：将硅负极材料(粒径100nm)与本实施例制备得到的锂离子电池用导电粘结剂G-PVA-b-PAALi按照质量比93:7在水中混合均匀得到负极浆料，将所得负极浆料涂于铜箔集流体上，110℃真空烘干，得到负极电极片，然后在手套箱中组装成扣式电池进行测试，其中，对电极采用锂金属，隔膜为celgard C2400，电解液为1.3M LiPF6的EC、PC和DEC(体积比为3:1:6)溶液。
实施例四
一种锂离子电池用导电粘结剂的制备方法，包括以下步骤：
(1)称取10g石墨烯，与100g浓硝酸(65wt％)水溶液混合后，加热至95℃，搅拌4h后，水洗干燥，得到氧化石墨烯样品G。
(2)将10g氧化石墨烯搅拌下分散于100ml四氢呋喃(THF)中，加入1g乙硼烷，室温下搅拌12h，将氧化石墨烯表面的羧基、酸酐、羰基等还原为醇羟基；然后用THF洗涤并干燥后，重新分散于2g吡啶与100mL干燥乙醚的混合溶液中，加入2g 2-溴异丁基酰溴(BiBB)，0℃下缓慢搅拌2h，然后再在室温下搅拌反应10h，经无水乙醇洗涤后干燥，得到羟基溴化的氧化石墨烯G-Br；
(3)将100mL甲醇、4g甲基丙烯酸甲酯、0.03g溴化亚铜(CuBr)、0.06g 2,2’-联吡啶(Bpy)加入反应器中，室温下进行氩气鼓泡30min除去体系中的氧；然后在氩气保护气氛下，加入上述G-Br粉末，密闭反应器在室温下搅拌反应18h，反应后过滤，以无水甲醇洗涤干燥，得到聚甲基丙烯酸甲酯接枝改性的石墨烯样品G-PMMA，即得到锂离子电池用导电粘结剂。
该产物可在锂离子电池石墨、硅及其合金等负极材料的浆料制备过程中，作为导电剂和粘结剂使用。
锂离子电池的制备：将硅负极材料(粒径100nm)与本实施例制备得到的锂离子电池用导电粘结剂G-PVA-b-PAALi按照质量比93:7在水中混合均匀得到负极浆料，将所得负极浆料涂于铜箔集流体上，110℃真空烘干，得到负极电极片，然后在手套箱中组装成扣式电池进行测试，其中，对电极采用锂金属，隔膜为celgard C2400，电解液为1.3M LiPF6的EC、PC和DEC(体积比为3:1:6)溶液。
效果实施例
为对本发明实施例技术方案带来的有益效果进行有力支持，特提供以下性能测试：
首次充放电效率和容量保持率测试：
(1)将实施例一扣式电池以100mA/1g活性物质的电流充电至电压为0.001V，接着恒压直至电流小于10mA/1g活性物质；搁置10mins；再将上述扣式电池以100mA/1g活性物质的电流放电至2.5V。完成上述充、电放电过程记为1个充/电放电循环。记录电池的首次充放电容量和循环充放电50次的充放电容量。
(2)将实施例二扣式电池以100mA/1g活性物质的电流充电至电压为4.4V，接着恒压直至电流小于10mA/1g活性物质；搁置10mins；再将上述扣式电池以100mA/1g活性物质的电流放电至3.0V。完成上述充、电放电过程记为1个充/电放电循环。记录电池的首次充放电容量和循环充放电50次的充放电容量。
电池的首次库伦效率和容量保持率的公式分别如下：
首次库伦效率(％)＝首次放电容量/首次充电容量×100％；
第n次循环的容量保持率(％)＝第n次循环的放电容量/第1次循环的放 电容量×100％。
实施例一扣式电池和实施例二扣式电池的首次充放电效率和容量保持率的测试结果如表1所示：
表1
Figure PCTCN2016108780-appb-000001
由上述可知，本发明实施例制备得到的锂离子电池用导电粘结剂可以有效缓冲充放电过程中活性材料的体积变化带来的负面影响，提高电池的循环特性，且该锂离子电池用导电粘结剂同时作为导电剂和粘结剂，可提高正负极嵌锂活性物质含量，进而提升电芯能量密度。

Claims (14)

  1. 一种锂离子电池用导电粘结剂，其特征在于，包括石墨烯以及接枝在所述石墨烯表面的第一粘结剂，所述第一粘结剂包括聚乙烯醇、羧甲基纤维素钠、聚乙二醇、聚乳酸、聚甲基丙烯酸甲酯、聚苯乙烯、聚偏氟乙烯、六氟丙烯聚合物、苯乙烯-丁二烯橡胶、海藻酸钠、淀粉、环糊精和多聚糖中的至少一种。
  2. 如权利要求1所述的锂离子电池用导电粘结剂，其特征在于，当所述第一粘结剂为聚乙烯醇、羧甲基纤维素钠、聚乙二醇、海藻酸钠、淀粉、环糊精和多聚糖中的至少一种时，所述锂离子电池用导电粘结剂进一步包括接枝在所述石墨烯表面的第二粘结剂，所述第二粘结剂通过化学键与所述第一粘结剂连接，所述第二粘结剂为聚丙烯酸和聚酰亚胺中的至少一种。
  3. 如权利要求1或2所述的锂离子电池用导电粘结剂，其特征在于，所述第一粘结剂和所述第二粘结剂中的羧基均为碱金属化羧基。
  4. 如权利要求1所述的锂离子电池用导电粘结剂，其特征在于，所述石墨烯粒子厚度为0.35-50nm，D50粒径为50-5000nm。
  5. 如权利要求1所述的锂离子电池用导电粘结剂，其特征在于，所述石墨烯占所述锂离子电池用导电粘结剂总质量的0.1-10％。
  6. 如权利要求2所述的锂离子电池用导电粘结剂，其特征在于，所述第一 粘结剂占所述第一粘结剂和所述第二粘结剂总质量的20-50％。
  7. 一种锂离子电池用导电粘结剂的制备方法，其特征在于，包括以下步骤：
    取石墨烯进行氧化处理后得到氧化石墨烯；取第一粘结剂，通过缩合反应使所述第一粘结剂接枝到所述氧化石墨烯表面；或取第一粘结剂的单体，通过原子转移自由基聚合反应使所述第一粘结剂的单体聚合接枝到所述氧化石墨烯表面，得到第一粘结剂接枝改性的石墨烯，即得到所述锂离子电池用导电粘结剂；所述第一粘结剂包括聚乙烯醇、羧甲基纤维素、聚乙二醇、聚乳酸、聚甲基丙烯酸甲酯、聚苯乙烯、聚偏氟乙烯、六氟丙烯聚合物、苯乙烯-丁二烯橡胶、海藻酸钠、淀粉、环糊精和多聚糖中的至少一种。
  8. 如权利要求7所述的锂离子电池用导电粘结剂的制备方法，其特征在于，当所述第一粘结剂为聚乙烯醇、羧甲基纤维素钠、聚乙二醇、海藻酸钠、淀粉、环糊精和多聚糖中的至少一种时，进一步包括在得到所述第一粘结剂接枝改性的石墨烯后，取第二粘结剂的单体，在引发剂的作用下，使所述第二粘结剂的单体原位聚合接枝到所述第一粘结剂接枝改性的石墨烯上，所述第二粘结剂通过化学键与所述第一粘结剂连接，得到所述锂离子电池用导电粘结剂；所述第二粘结剂为聚丙烯酸和聚酰亚胺中的至少一种。
  9. 如权利要求8所述的锂离子电池用导电粘结剂的制备方法，其特征在于，所述引发剂选自过硫酸铵、过硫酸碱金属盐、偶氮二异丁腈、过氧化苯甲酰、偶氮二异丁基脒盐酸盐、偶氮二氰基戊酸和偶氮二异丙基咪唑啉中的至少一种。
  10. 如权利要求7或8所述的锂离子电池用导电粘结剂的制备方法，其特征在于，当所述第一粘结剂包括聚乳酸时，或当所述第二粘结剂包括聚丙烯酸时，进一步包括采用碱金属氢氧化物水溶液将所述聚乳酸或聚丙烯酸中的羧基进行碱金属化处理。
  11. 一种锂离子电池电极极片，其特征在于，包括集流体，以及涂覆在所述集流体上的电极活性材料和如权利要求1-6任一项所述的锂离子电池用导电粘结剂。
  12. 如权利要求11所述的锂离子电池电极极片，其特征在于，所述锂离子电池用导电粘结剂占所述电极活性材料与所述锂离子电池用导电粘结剂总质量的0.5-10％。
  13. 一种锂离子电池电极极片的制备方法，其特征在于，包括以下步骤：
    取集流体，将电极活性材料和如权利要求1-6任一项所述的锂离子电池用导电粘结剂加入到溶剂中，混合均匀，得到浆料，将所述浆料涂敷在所述集流体上，于90-120℃烘干后压制，得到锂离子电池电极极片。
  14. 一种包含如权利要求1-6任一项所述的锂离子电池用导电粘结剂的锂离子电池。
PCT/CN2016/108780 2016-05-12 2016-12-07 一种锂离子电池用导电粘结剂及其制备方法、锂离子电池电极极片及制备方法和锂离子电池 WO2017193571A1 (zh)

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