SE2250822A1 - Binder combination for a secondary cell - Google Patents

Binder combination for a secondary cell

Info

Publication number
SE2250822A1
SE2250822A1 SE2250822A SE2250822A SE2250822A1 SE 2250822 A1 SE2250822 A1 SE 2250822A1 SE 2250822 A SE2250822 A SE 2250822A SE 2250822 A SE2250822 A SE 2250822A SE 2250822 A1 SE2250822 A1 SE 2250822A1
Authority
SE
Sweden
Prior art keywords
binder
electrode
secondary cell
silicon
chitosan
Prior art date
Application number
SE2250822A
Inventor
Parth Omprakash Dayama
Prasad Mangesh Korde
Original Assignee
Northvolt Ab
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Northvolt Ab filed Critical Northvolt Ab
Priority to SE2250822A priority Critical patent/SE2250822A1/en
Priority to PCT/EP2023/067680 priority patent/WO2024003155A1/en
Publication of SE2250822A1 publication Critical patent/SE2250822A1/en

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
    • 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
    • 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
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
    • H01M50/121—Organic material
    • 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
    • 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
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane

Abstract

An electrode binder, wherein the binder comprises a chitosan-grafted polyaniline copolymer; and a polymer selected from any one of a styrene-butadiene rubber and carboxymethylcellulose, or a combination of these; as well as an electrode comprising such binder; a secondary cell comprising comprising such binder; and a vehicle comprising such secondary cell.

Description

FIELD OF THE INVENTION The present disclosure relates to an electrode binder for an electrode in a secondary cell. More particularly, the present disclosure relates to a binder combination comprising a chitosan- grafted-polyaniline copolymer in combination with carboxymethylcellulose or styrene- butadiene rubber, an electrode comprising the binder combination, a secondary cell comprising such electrode, as well as a vehicle comprising such secondary cell.
TECHNICAL BACKGROUND Rechargeable batteries having high energy density and discharge voltage, in particular Li-ion batteries, are a vital component in portable electronic devices and are a key enabler for the electrification of transport and large-scale storage of electricity. To reach higher energy densities, new types of batteries are being developed.
State of the art Li-ion batteries typically consist of stacks of secondary cells, wherein each cell is composed of a cathode comprising a cathode current collector, an electrolyte, an anode comprising an anode current collector, and optionally a separator positioned between the anode and cathode.
One of the limiting factors of the Li-ion battery is its anode. ln secondary cells where the anode is made of graphite-based materials, the cations extracted from the cathode material diffuse from the cathode material through the electrolyte and intercalate into the graphite material at the anode during charging. During discharge, this process is reversed. ln an effort to increase the energy density of the secondary cells, development is ongoing to replace a part of the graphite with silica to increase the capacity of the electrode since silica demonstrates a higher maximum theoretical capacity than graphite. However, a challenge with silica is that it swells and contracts during charge and discharge. This causes a mechanical stress in the electrode material, which may initiate cracks and also impair the adhesion of the electrode active material to the current collector leading to electrode disintegration. These circumstances may shorten the performance and lifetime of the secondary cell.
Attempts have been made to use a binder to achieve better adherence of the electrode active material and conducting agent to the current collector and improve the mechanical strength of the anode. Conventional binders used for electrodes in batteries are poly-(vinylidene fluoride) (PVDF), copolymers of vinylidene difluoride (VdF) and hexafluoropropene (HFP) monomers (Kynar or KynarFlex), carboxymethylcellulose (CMC) and its sodium salt (C|\/IC-Na), po|y(acry|ic acid) (PAA) and its sodium salt (PAA-Na), and styrene-butadiene rubber (SBR). Polyvinylidene fluoride and styrene-butadiene rubber possess a weak interaction with si|icon and are ineffective in reducing volume changes of si|icon material. Sodium carboxymethylcellulose and po|y(acry|ic acid) are rather brittle.
Hence, there is a need for improving the mechanical integrity of the electrodes and at the same time improving the electric conductivity.
SUMMARY OF THE INVENTION An object of the present invention is to provide an electrode binder for an electrode in a secondary cell, wherein the binder may provide an improved electric conductivity and a good mechanical strength to maintain the structure ofthe electrode. A further object is the provision of an anode electrode with an improved electrochemical performance and low swelling.
The present invention provides a binder combination for an electrode in a secondary cell, wherein the binder comprises a chitosan-grafted-polyaniline copolymer in combination with carboxymethylcellulose or styrene-butadiene rubber.
DETAILED DESCRIPTION OF THE INVENTION ln a first aspect, the present invention relates to an electrode binder for an electrode in a secondary cell, wherein the binder comprises a chitosan-grafted-polyaniline copolymer (CS-g-PANI) and a polymer selected from any one of styrene-butadiene rubber (SBR), carboxymethylcellulose (C|\/IC), or a combination of these.
Preferably, the electrode binder is a binder for an anode.
A chitosan-grafted-polyaniline copolymer is formed by graft polymerization of chitosan and polyaniline and has a high degree of cross-linking. Chitosan is a polysaccharide obtained by deacetylation of chitin from crustaceans and insects, and contributes to the mechanical stability. Polyaniline is a conducting polymer derived from ani|ine monomers and helps to improve the electric conductivity of the binder. Preferably the ratio of chitosan to polyaniline in the chitosan-grafted-polyaniline copolymer used herein is from about 30:70 to about 70:30, or from about 40:60 to about 60:40 (mass ratio chitosan:po|yani|ine). Preferably the ratio of chitosan to polyaniline in the chitosan-grafted-polyaniline copolymer used herein is about 50:50. The chitosan-grafted-polyaniline copolymer adheres strongly to silicon and may provide for less degradation of a silicon-based electrode.
Styrene-butadiene rubber is an elastomeric binder derived from styrene and butadiene. Preferably the ratio of styrene to butadiene in the styrene-butadiene rubber used herein is from about 20:80 to about 30:70 (molar parts styrene:butadiene), preferably from about 24:76 to about 26:74. The styrene-butadiene rubber is flexible and may suppress the formation of cracks in the electrode material.
Ca rboxymethyl cellulose is a water-soluble derivative of cellulose wherein some of the hyd roxyl groups in the anhydroglucose units of cellulose have been substituted with carboxymethyl groups (-CH2-COOH). The average number of substituted hydroxyl groups per anhydroglucose unit is defined as the degree of substitution (DS). Preferably the degree of substitution of the carboxymethyl cellulose is not more than 3, such as from 1 to 3. The carboxymethyl cellulose affects the flow behavior and processing properties of the binder.
Preferably, the binder comprises a combination of a chitosan-grafted polyaniline copolymer, a styrene-butadiene rubber and carboxymethylcellulose. Such a binder prevents swelling of a silicon-based electrode. ln one embodiment the binder comprises from about 30 to about l60l[HD1]AÉ[PK2]% (w/w) of a chitosan-grafted polyaniline copolymer, from about 20 to about 35% (w/w) styrene-butadiene rubber and from about 20 to about 35% (w/w) carboxymethylcellulose, up to a total of component parts of 100%.
The polymers used in the binder of the present invention are water-processable and thus more environmentally benign and are also relatively inexpensive in comparison with many other binder polymers requiring cumbersome processing, involving inter a/ia the use of hazardous and high-boiling solvents, which use are often associated with higher costs.
Another aspect of the invention is an electrode comprising the binder according to the first aspect of the present invention. Preferably, the electrode is a silicone-graphite electrode comprising graphite and a silicon-based material. ln one embodiment, the silicon-based lmaterial is selected from any one of silicon, silicon alloy, silicon oxide (SiOX), and lithiated SiOX, wherein x is from 1 to 2; or a combination of at least two of these. Preferably, the silicon-based material is selected from silicon or silicon oxide. Preferably, the amount of silicon orÉ [PK3]silicon-oxide in the silicone-graphite electrode is at least about 10% (w/w), or at least about 30% (w/w), or at about least 40% (w/w), and up to at most about 50% (w/w), or at most about 60% (w/w) . ln one embodiment, the silicone-graphite electrode is adhered to a current collector. The current collector may be in the form of a foil, or in the form of a mesh. ln one embodiment, the foil is coated with a material that has been chosen from the group consisting of C, Si, Sn, Al, Zn, Ag, ln, Mg.
Preferably, the electrode is an anode. ln a further aspect, the present invention relates to a secondary cell comprising an anode, a cathode, an electrolyte, and optionally a separator, characterized in that the secondary cell further comprises a binder in the anode, wherein the binder comprises a chitosan-grafted polyaniline copolymer; and a polymer selected from any one of a styrene-butadiene rubber and carboxymethylcellulose, or a combination of these.
The electrolyte used in the secondary cell according to the present invention is a liquid electrolyte comprising at least one lithium salt and at least one or more solvents selected from the group consisting of carbonate solvents and their fluorinated equivalents, diC1.4 ethers and their fluorinated equivalents and ionic liquids. The lithium salt is preferably one or more selected from the group consisting of lithium hexafluorophosphate (LiPF6), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium (fluorosulfonyl)(trifluoromethanesulfonyl)imide (LiFTFSI), lithium bis(pentafluoroethanesulfonyl)imide (LiBETI), lithium (pentafluoroethanesulfonyl)(trifluoromethanesulfonyl)imide (LiPTFSI), lithium trifluoromethanesulfonate (LiOTf), lithium bis(oxa|ato)borate (LiBOB), lithium dif|uoro(oxa|ato)borate (LiDFOB), lithium difluorobis(oxalato)phosphate (LiDFOP), lithium tetrafluoro(oxalato)phosphate (LiTFOP), lithium tetrafluoroborate (LiBF4), lithium nitrate (LiNOg) lithium 2-trifluoromethyl-4,5-dicyanoimidazole (LiTDI). ln one embodiment, the solvent is selected from the group consisting of 1,2-dimethoxyethane (DME), N-propyl-N- methylpyrrolidinium bis(fluorosulfonyl)imide (PYR13-FSI), N-propyl-N-methylpyrrolidinium bis trifluoromethanesulfonyl)imide (PYR13-TFSI), 1-butyl-1-methylpyrrolidinium ( bis(fluorosulfonyl)imide (PYR14-FSI), 1-butyl-1-methylpyrrolidinium ( ( bis trifluoromethanesulfonyl)imide (PYR14-TFSI), 1-ethyl-3-methylimidazolium bis fluorosulfonyl)imide (EMIM-FSI), 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (E|\/|||\/I-TFSI), dimethyl carbonate (DMC), ethyl methyl ca rbonate (EMC), diethyl carbonate (DEC), ethylene carbonate (EC), and propylene carbonate (PC), and their fluorinated equivalents. ln a further aspect, the present invention relates to a vehicle comprising a secondary cell according to the previous aspect of the present invention.
As used herein, the term "about" refers to a value or parameter herein that includes (and describes) embodiments that are directed to that value or parameter per se. For example, description referring to "about 50" includes description of "50." Numeric ranges are inclusive of the numbers defining the range. Generally speaking, the term "about" refers to the indicated value of the variable and to all values of the variable that are within the experimental error of the indicated value (e.g., within the 95% confidence interval for the mean) or within 10 percent of the indicated value, whichever is greater.
All aspects and embodiments disclosed herein can be combined with any other aspect and/or embodiment disclosed herein.

Claims (1)

1.Claims An electrode binder, wherein the binder comprises a chitosan-grafted polyaniline copolymer; and a polymer selected from any one of a styrene-butadiene rubber, carboxymethylcellulose, or a combination of these. The binder according to claim 1, wherein the binder comprises a combination of a chitosan- grafted polyaniline, a styrene-butadiene rubber and carboxymethylcellulose. The binder according to claim 1 or 2, which is a binder for an anode. An electrode comprising the binder according to claim 1 or The electrode according to claim 4, wherein the electrode is a silicon-graphite-electrode, comprising graphite and a silicon-based material. The electrode according to claim 5, wherein the silicon-based material is selected from any one of Si or SiOx, or a combination thereof, wherein x is from 1 to The electrode according to claim 5 or 6, wherein the amount of the silicon-based material is at least about 10% (w/w). The electrode according to claim 5 or 6, wherein the amount of the silicon-based material is at least about 30% (w/w). The electrode according to any one of claims 4-8, which is an anode. A secondary cell comprising an anode, a cathode, an electrolyte, and optionally a separator, characterized in that the secondary cell further comprises a binder in the anode, wherein the binder comprises a chitosan-grafted polyaniline copolymer; and a polymer selected from any one of a styrene-butadiene rubber and carboxymethylcellulose, or a combination of these. A vehicle comprising the secondary cell according to claim 10, wherein the secondary cell further comprises a lithium nickel manganese cobalt oxide cathode.
SE2250822A 2022-06-30 2022-06-30 Binder combination for a secondary cell SE2250822A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
SE2250822A SE2250822A1 (en) 2022-06-30 2022-06-30 Binder combination for a secondary cell
PCT/EP2023/067680 WO2024003155A1 (en) 2022-06-30 2023-06-28 Binder combination for a secondary cell

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
SE2250822A SE2250822A1 (en) 2022-06-30 2022-06-30 Binder combination for a secondary cell

Publications (1)

Publication Number Publication Date
SE2250822A1 true SE2250822A1 (en) 2023-12-31

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SE (1) SE2250822A1 (en)
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150108410A1 (en) * 2012-07-13 2015-04-23 Guangzhou Institute Of Energy Conversion, Chinese Academy Of Sciences Chitosan-based binder for electrodes of lithium ion batteries
CN108183235B (en) * 2017-11-17 2020-07-17 合肥国轩高科动力能源有限公司 Modified styrene-butadiene rubber type negative electrode binder
KR102154194B1 (en) * 2019-04-29 2020-09-09 인천대학교 산학협력단 A graft copolymer, a method for producing the same, a binder for a silicon anode including the same, a silicon anode including the binder for the silicon anode, and a lithium ion battery including the silicon anode
CN108232152B (en) * 2017-12-29 2021-04-06 银隆新能源股份有限公司 Battery anode slurry, battery anode and battery
CN113675479A (en) * 2021-10-21 2021-11-19 惠州市纬世新能源有限公司 Preparation process and application of gel lithium battery

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NO20151278A1 (en) * 2015-09-29 2017-03-30 Elkem As Silicon-carbon composite anode for lithium-ion batteries

Patent Citations (5)

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US20150108410A1 (en) * 2012-07-13 2015-04-23 Guangzhou Institute Of Energy Conversion, Chinese Academy Of Sciences Chitosan-based binder for electrodes of lithium ion batteries
CN108183235B (en) * 2017-11-17 2020-07-17 合肥国轩高科动力能源有限公司 Modified styrene-butadiene rubber type negative electrode binder
CN108232152B (en) * 2017-12-29 2021-04-06 银隆新能源股份有限公司 Battery anode slurry, battery anode and battery
KR102154194B1 (en) * 2019-04-29 2020-09-09 인천대학교 산학협력단 A graft copolymer, a method for producing the same, a binder for a silicon anode including the same, a silicon anode including the binder for the silicon anode, and a lithium ion battery including the silicon anode
CN113675479A (en) * 2021-10-21 2021-11-19 惠州市纬世新能源有限公司 Preparation process and application of gel lithium battery

Non-Patent Citations (2)

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Title
Kim E; Rajeev K K; Nam J; Kim T -H, "Chitosan-: Grafted -poly(aniline- co -anthranilic acid) as a water soluble binder to form 3D structures for Si anodes" 2020, vol. 10, nr. 13, pp 7643 - 7653 *
Rajeev K K; Kim Eunsoo; Nam Jaebin; Lee Suhyun; Mun Junyoung; Kim Tae-Hyun "Chitosan-grafted-polyaniline copolymer as an electrically conductive and mechanically stable binder for high-performance Si anodes in Li-ion batteries" Electrochimica Acta 2019, vol. 333, p. 135532 *

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