WO2023249567A1 - Lithium-ion battery with positive electrode containing nmc material as the core and carbon black as the shell - Google Patents

Lithium-ion battery with positive electrode containing nmc material as the core and carbon black as the shell Download PDF

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Publication number
WO2023249567A1
WO2023249567A1 PCT/TH2023/050009 TH2023050009W WO2023249567A1 WO 2023249567 A1 WO2023249567 A1 WO 2023249567A1 TH 2023050009 W TH2023050009 W TH 2023050009W WO 2023249567 A1 WO2023249567 A1 WO 2023249567A1
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per
lithium
positive electrode
core
carbon black
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PCT/TH2023/050009
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French (fr)
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WO2023249567A4 (en
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Atiweena KRITTAYAVATHANANON
Harnchana GATEMALA
Sunee WONGCHITPHIMON
Komkrit SUTTIPONPARNIT
Thanaporn PIMSUWAN
Wannaporn WANGSIRISUNTORN
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Ptt Public Company Limited
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Publication of WO2023249567A1 publication Critical patent/WO2023249567A1/en
Publication of WO2023249567A4 publication Critical patent/WO2023249567A4/en

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    • 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
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    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
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    • 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
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    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • 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
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • NMC nickel manganese cobalt
  • a battery is an energy-retaining device capable of converting chemical energy to electrical power.
  • Batteries can be divided into two types, namely primary batteries that are disposable and secondary batteries that are rechargeable.
  • Popular secondary batteries at present are lithium-ion ones, which use lithium in the form of inorganic compounds capable of generating electrical power from lithium ions’ mobility.
  • Lithium-ion batteries are highly popular for electronic and portable electrical devices as well as in electrical vehicle industry. Lithium-ion batteries can be produced in several forms according to their use, such as button cells, cylindrical cells, pouch cells and prismatic cells. In addition, there are battery packs used for massive electrical power generation, such as those in electrical vehicles, etc.
  • a lithium-ion battery cell consists of a positive electrode, an negative electrode, electrolyte solution and a separator.
  • the positive electrode contains positive electrode active material, which can absorb and emit lithium ions, made from a lithium-containing material, such as lithium cobalt oxide LiCoCh), which is the first positive electrode active material in positive electrode production for lithium-ion batteries, but its safety is found to be low; lithium manganese oxide (LiM CU) with high thermal stability, with safety but low cycle life; lithium iron phosphate (LiFePCU) with high safety, small size, high stability and high use cycles but lower energy density than that of other types of lithium batteries.
  • LiCoCh lithium cobalt oxide
  • NMC material LiNMC or NMC
  • NiMC111 is LiNMC containing nickel per manganese per cobalt at 1 per 1 per 1
  • NMC811 contains nickel per manganese per cobalt at 8 per 1 per 1.
  • the LiNMC utilises good properties of nickel, manganese and cobalt.
  • nickel has high specific energy but low stability while manganese has low internal resistance. Combination of these elements provides the lithium material with strength and thermal stability, fit for use requiring high battery capacity and low heat generation rate like in electrical vehicles.
  • positive electrode active material has been made from NMC material formed in a structure containing metal oxide as the core, with the shell (core-shell particle, core@shell), where the external shell helps increase energy from electrolyte- adsorbing surface and increase electrical conductivity that may affect batteries’ performance and useful life.
  • inventions have been disclosed in various patents. For example:
  • a Chinese patent application number CN108539193A has invented a positive electrode with positive electrode active material containing NMC material as the core and carbon nanotube as the shell with the proportion of carbon nanotube shell of 0.01 to 5% by weight of the NMC material core, where particle sizes of NMC material core are 5- 15 microns.
  • the invented positive electrode has the electric charge of 2.5-4.5 V, the initial charge/ discharge rate greater than 240 mAh/g (milliampere-hour per gram) and the capacity retention ratio of 90 percent at 100 charge cycles.
  • a Chinese patent application number CN111354936A has produced a positive electrode containing NMC material as the core, and the shell of carbon containing nanosized magnesium oxide or aluminium oxide.
  • a Chinese patent application number CN112331830A has presented the invention of lithium-ion battery’s positive electrode in the form containing NMC material as the core, and the shell.
  • the NMC material core can be selected from NMC 111, NMC532 or NMC811 , and graphene is used as the shell, where the ratio of NMC material core per the graphene shell is 1 per 0.005-0.1, and the ratio of NMC material core and graphene shell per acetylene black- type conductive material per polyvinylidene fluoride (PVDF)-type binder used is 80 per 10 per 10.
  • PVDF polyvinylidene fluoride
  • Negative electrodes have diverse compositions and are an important variable affecting batteries’ performance and properties.
  • Negative electrodes, the electrolyte solution and separators also are critical. Negative electrodes contain negative electrode active material being carbon, such as graphite or nanocarbon, or lithium- containing material. Negative electrode production may combine the negative electrode active material with conductive material and binder for enhancing the negative electrode’s performance.
  • the electrolyte solution contains lithium salts; generally popular ones of which are lithium hexafluorophosphate (LiPFe), lithium tetrafluoroborate (LiBF4), lithium bis(fluorosulfonyl) imide (LiFSI), etc.
  • lithium salts are dissolved in organic solution, such as ethylene carbonate (EC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), propylene carbonate (PC), etc.
  • organic solution such as ethylene carbonate (EC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), propylene carbonate (PC), etc.
  • separators which keep the positive electrode and negative electrode apart to avoid contact, generally being polymers, such as polyethylene (PE) , polypropylene (PP), etc.
  • PE polyethylene
  • PP polypropylene
  • a US patent application number US20210159541A1 has invented a battery with positive electrode using positive electrode active material being NMC111 material combined with conductive carbon and a polyvinylidene fluoride (PVDF)-type binder, and negative electrode using negative electrode active material being artificial graphite combined with styrene-butadiene rubber (SBR) and carboxymethyl cellulose (CMC).
  • Electrolyte solution is used, where lithium salts are lithium hexafluorophosphate ( LiPFe) , lithium bis( fluoro sulfonyl) imide ( LiFSI) and lithium tetrafluoroborate (LiBEp at the ratio of 1 per 0.01- 1.2 per 0.05-0.7 by mole, respectively.
  • LiPFe lithium hexafluorophosphate
  • LiFSI lithium bis( fluoro sulfonyl) imide
  • LiBEp lithium tetrafluoroborate
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • DMC dimethyl carbonate
  • VC vinylene carbonate
  • FEC fluoroethylene carbonate
  • PS propane sultone
  • a European patent application number EP39168504A4 has used an negative electrode active material being artificial graphite, and a US patent number US 11152621B2 has used negative electrode’ s retaining material being artificial graphite but with surface improvement by nitrogen atom addition.
  • a US patent number US 10897062B2 has produced a battery with positive electrode containing NMC material; negative electrode containing graphite coated with amorphous carbon; lithium bis( fluoro sulfonyl) imide (LiFSI) and lithium hexafluorophosphate (LiPFe) electrolyte solution in a solvent mixture of ethylene carbonate (EC), ethyl methyl carbonate (EMC) and dimethyl carbonate (DMC); and a lithium difluorophosphate (LiPO2F2) additive.
  • LiFSI lithium bis( fluoro sulfonyl) imide
  • LiPFe lithium hexafluorophosphate
  • PVDF polyvinylidene fluoride
  • the batteries were produced as 18650 cylindrical cells, using a ratio of NMC material as the core with nanocarbon as the shell per carbon black as the conductive material per poly vinylidene fluoride (PVDF) of 946 per 24 per 3 by weight, respectively.
  • the electrolyte solution was used that contained 10 molar lithium hexafluorophosphate (LiPFe) in solvents of ethylene carbonate (EC) combined with dimethyl carbonate (DMC) at a ratio of 1 per 1 by volume, respectively.
  • the negative electrode was used that consisted of graphite-type negative electrode active material, carbon black as a conductive material and poly vinylidene fluoride (PVDF) as a binder at a ratio of 96.6 per 1.7 per 1.7 by weight, respectively.
  • button cells were invented, using lithium as the negative electrode, with the positive electrode containing NMC material as the core and nanocarbon as the shell per carbon black as the conductive material per poly vinylidene fluoride at 80 per 10 per 10 by weight, respectively.
  • a Thai patent application number 1601000751 has invented a positive electrode of lithium sulfur battery in the form of structure containing the core and shell, using sulfur as the core and nanocarbon as the shell at a ratio of 95 per 5 by weight, respectively, and using mechanofusion for forming materials into the core and shell structure with a ratio of positive electrode containing sulfide with nanocarbon as the shell per nanocarbon- type conductive material per poly vinylidene fluoride (PVDF)-type binder of 6 per 3 per 1 by weight, respectively.
  • PVDF poly vinylidene fluoride
  • a thai patent application number 1601000853 has invented an electrode, consisting of NMC material as positive electrode active material with a ratio of positive electrode active material per nanocarbon-type conductor per polyvinylidene fluoride (PVDF)-type binder of 8 per 1 per 1 by weight, respectively.
  • PVDF polyvinylidene fluoride
  • a Thai patent application number TH 1601001280 has invented lithium-ion battery's positive electrode in the form of structure having a core and a shell, using lithium polysulfide as the core and nanocarbon as the shell at a ratio of 95 per 5 by weight, respectively, and a ratio of positive electrode consisting of lithium sulfide with nanocarbon as the shell per nanocarbon- type conductive material per poly vinylidene fluoride (PVDF)-type binder at 6 per 3 per 1 by weight, respectively.
  • PVDF poly vinylidene fluoride
  • a Thai patent application number 1801007531 has invented a positive electrode of lithium- ion battery in a form with positive electrode active material containing lithium nickel aluminium oxide as the core and nanocarbon as the shell at the ratio of 70-95 per 5-30 by weight, respectively.
  • a Thai patent application number 1801005876 has presented a manufacturing process for lithium-ion battery’s electrode, where positive electrode contains lithium metal silicate mixed with carbon-type conductor and binder, such as polyvinylidene fluoride (PVDF).
  • PVDF polyvinylidene fluoride
  • the obtained mixture is coated on aluminium foil, and the obtained lithium-ion battery has initial electrical discharge of 1,950 mAh/g at a battery discharge rate (C rate) of 0.05.
  • a Thai patent application number 1501005436 has invented an negative electrode, using negative electrode active material being silicon, graphene as a conductor and polyacrylic acid as a binder at the ratio of 15-85 per 3-75 per 3-60 by weight, respectively.
  • this invention has developed a positive electrode with positive electrode active material containing NMC material core and carbon black shell, improved electrolyte solution for the enhanced performance, using additive that helps minimise undesirable reactions that may produce gases in the system and affect the useful life, and also optimised negative electrode compositions of battery.
  • the core uses NMC material (LiNMC or NMC), and carbon black is used as the shell, where the positive electrode uses the ratio of NMC material as the core per carbon black as the shell ranging from 95.01 per 4.99 to 99.5 per 0.5 parts by weight.
  • electrolyte solution is provided such that it has a property to minimise gas pores with use of additive.
  • the prepared positive electrode is coated on aluminium foil.
  • FIG. 1 The capacity retention (percentage) upon use of pouch cells with use of 2% vinylene carbonate (VC) and 0- 10% fluoroethylene carbonate ( FEC) additives by weight of electrolyte solution.
  • VC vinylene carbonate
  • FEC fluoroethylene carbonate
  • Figure 3 The capacity retention (percentage) upon use of pouch cells with use of 2% vinylene carbonate (VC) and 0.1% fluoroethylene carbonate (FEC) additives by weight of electrolyte solution at battery charge/discharge rates (C -rates) of 0.5C and 1.0C.
  • VC vinylene carbonate
  • FEC fluoroethylene carbonate
  • This invention discloses the lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell and the manufacturing process of the said battery as follows.
  • the positive electrode contains the positive electrode active material, which can absorb and emit lithium ions, made from a lithium- containing material in the form of core- shell particle (core@ shell), where the metal oxide core is Lithium Nickel Manganese Cobalt Oxide (NMC material or LiNMC or NMC) and the shell is carbon black with the ratio of NMC material as the core per carbon black as the shell ranging from 95.01 per 4.99 to 99.5 per 0.5 parts by weight, respectively.
  • the preferred ratio ranges from 98 per 2 to 99 per 1 parts by weight, respectively.
  • the most preferable ratio is 99 per 1 parts by weight, respectively.
  • the positive electrode further comprises carbon as conductive material, and binder used for positive electrode, which has composition ratio of NMC material core and carbon black shell (NMC@C)per carbon used as the conductive material per the binder of 80-99 per 0.5-10 per 0.5-10 parts by weight, respectively.
  • the best composition ratio of NMC material core and carbon black shell (NMC@C) per carbon used as the conductive material per the binder is 94 per 4 per 2 parts by weight, respectively.
  • Carbon used as the conductive material can be selected from any one of carbon black, nanocarbon, graphite or combination thereof, where the best carbon used as the conductive material is carbon black.
  • the binder for the positive electrode can be selected from any one of polyvinylidene fluoride ( PVDF) , carboxymethyl cellulose ( CMC) , sodium carboxymethyl cellulose, butadiene rubber, styrene- butadiene rubber ( SBR) , poly( vinyl alcohol) ( PVA) or polyacrylic acid or combination thereof, where the most preferable binder for the positive electrode is polyvinylidene fluoride (PVDF).
  • the negative electrode contains any one of graphite-type carbon, oxide material or lithium or combination thereof to form the negative electrode active material, depending on the form of invented lithium-ion battery, where the preparation of negative electrode from either graphite-type carbon or oxide material or both comprises carbon as the conductive material, and binder used for negative electrode.
  • the most preferable graphite-type carbon is artificial graphite.
  • Carbon used as the conductive material can be selected from any one of carbon black, nanocarbon, graphite or combination thereof, where the best carbon used as the conductive material is carbon black.
  • the binder for the negative electrode can be selected from any one of polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC) , sodium carboxymethyl cellulose, butadiene rubber, styrenebutadiene rubber (SBR), poly(vinyl alcohol) (PVA) or polyacrylic acid or combination thereof, where the most preferable binder for the negative electrode is either carboxymethyl cellulose (CMC) or styrene-butadiene rubber (SBR) or both.
  • PVDF polyvinylidene fluoride
  • CMC carboxymethyl cellulose
  • SBR styrenebutadiene rubber
  • PVA poly(vinyl alcohol)
  • polyacrylic acid or combination thereof where the most preferable binder for the negative electrode is either carboxymethyl cellulose (CMC) or styrene-butadiene rubber (SBR) or both.
  • the negative electrode has composition ratio of negative electrode active material being graphite- type carbon or oxide material per carbon used as the conductive material per carboxymethyl cellulose (CMC) per styrene-butadiene rubber (SBR) at 80-98.5 per 0.5-10 per 0.5-5 per 0.5-5 parts by weight, respectively.
  • the best composition ratio is 94.5 per 1 per 2.25 per 2.25 parts by weight, respectively.
  • the most preferable negative electrode active material is artificial graphite for preparing the negative electrode according to the mentioned compositions.
  • the electrolyte solution comprises a lithium salt and solvent, where:
  • the lithium salt is lithium hexafluorophosphate (LiPFe)in a concentration range of 1.0- 1.5 molars; the most preferable of which is 1.2 molars.
  • the solvent can be selected from any one of ethylene carbonate (EC), ethyl methyl carbonate (EMC) and dimethyl carbonate (DMC) or combination thereof, where the solvent ratio comprises ethylene carbonate (EC) per ethyl methyl carbonate (EMC) per dimethyl carbonate (DMC) at 5-30 per 5-40 per 30-90 parts by weight, and the best solvent ratio is 25 per 5 per 70 parts by weight, respectively.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • DMC dimethyl carbonate
  • the additive can be selected from any one of vinylene carbonate (VC), fluoroethylene carbonate ( FEC) , propane sultone ( PS) , lithium difluorophosphate ( LiPO2F2) , methylene methanedisulfonate (MMDS) or combination thereof in the amount of 0.1-12 percent by weight of electrolyte solution, where preferred additives comprise vinylene carbonate (VC) in the amount of 2 percent by weight of electrolyte solution, combined with any one of fluoroethylene carbonate ( FEC) , propane sultone ( PS) , lithium difluorophosphate LiPO2F2) , or methylene methanedisulfonate (MMDS) additives or combination thereof in the amount of 0.1- 10 percent by weight of electrolyte solution.
  • the most preferable additive amounts comprise vinylene carbonate (VC) at 2 percent combined with fluoroethylene carbonate (FEC) at 0.1 percent by weight of electrolyte solution.
  • the most preferable electrolyte solution comprises 1.2 molars lithium hexafluorophosphate in ethylene carbonate (EC) per ethyl methyl carbonate (EMC) per dimethyl carbonate (DMC) solvents at 25 per 5 per 70 parts by weight, respectively, and vinylene carbonate (VC) and fluoroethylene carbonate (FEC) additives in the amounts of 2 and 0. 1 percent by weight of electrolyte solution, respectively.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • DMC dimethyl carbonate
  • VEC vinylene carbonate
  • FEC fluoroethylene carbonate
  • the preparation of lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell comprises the following steps.
  • NMC lithium manganese cobalt oxide
  • the first process upon using the negative electrode active material being either graphite- type carbon or oxide material or both, contains a step of grinding graphite-type carbon or oxide material using high energy ball mill. Afterwards, add carbon used as the conductive material, binder and organic solvent, wherein the organic solvent can be selected from any one of N-methyl-2-pyrrolidone, ethanol or water or combination thereof; then coat the prepared negative electrode on copper foil; and then dry.
  • the organic solvent can be selected from any one of N-methyl-2-pyrrolidone, ethanol or water or combination thereof
  • the second process uses the negative electrode containing the negative electrode active material being lithium metal in the form of lithium metal sheet.
  • LiPFe lithium hexafluorophosphate
  • step D Assemble the lithium-ion battery using the positive electrode prepared from step A, the negative electrode prepared from step B, polymer film as a separator and the electrolyte solution as the ions transport as prepared from step C.
  • the positive electrode prepared and coated on aluminium foil has a weight range of 17-23 milligrams per square centimetre and a thickness range of 110-250 micrometres.
  • the negative electrode upon using the negative electrode active material being graphite- type carbon or oxide material as prepared and coated on the copper foil has a weight range of 10- 15 milligrams per square centimetre and a thickness range of 100-250 micrometres.
  • the positive electrode contains the positive electrode active material in the form of core- shell particle ( core @ shell) being NMC material (LiNMC or NMC) as the metal oxide core with carbon black shell (NMC@C) where the ratio of materials containing NMC material as the core per carbon black as the shell ranges from 95.01 per 4.99 to 99.5 per 0.5 parts by weight, respectively, the preferred ratio ranges from 98 per 2 to 99 per 1 parts by weight, respectively. The most preferable ratio is 99 per 1 parts by weight, respectively.
  • the positive electrode has the ratio of NMC material core and carbon black shell per carbon used as the conductive material per the binder at 80-99 per 0.5- 10 per 0.5- 10 parts by weight, respectively.
  • the best positive electrode’ s ratio is 94 per 4 per 2 parts by weight, respectively.
  • Carbon used as the conductive material can be selected from any one of carbon black, nanocarbon or graphite or combination thereof, where the best carbon used as the conductive material is carbon black.
  • the binder for the positive electrode can be selected from polyvinylidene fluoride ( PVDF) , carboxymethyl cellulose ( CMC) , sodium carboxymethyl cellulose, butadiene rubber, styrene-butadiene rubber, polycvinyl alcohol) (PVA) or polyacrylic acid or combination thereof, where the most preferable binder for the positive electrode is polyvinylidene fluoride (PVDF).
  • the first process’ negative electrode- preparing step upon using the negative electrode active material being either graphite- type carbon or oxide material or both comprises carbon used as the conductive material, and the binder used for the negative electrode.
  • the most preferable negative electrode active material of graphite-type carbon is artificial graphite; carbon used as the conductive material can be selected from any one of carbon black, nanocarbon, graphite or combination thereof, where the best carbon used as the conductive material is carbon black; and the binder for the negative electrode can be selected from any one of polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC), sodium carboxymethyl cellulose, butadiene rubber, styrene-butadiene rubber (SBR), poly(vinyl alcohol) (PVA) or polyacrylic acid or combination thereof, where the most preferable binder for the negative electrode is either carboxymethyl cellulose (CMC) or styrene-butadiene rubber (SBR) or both.
  • PVDF polyvinylidene fluor
  • the negative electrode has the preferred composition ratio comprising the negative electrode active material of graphite-type carbon or oxide material per carbon used as the conductive material per carboxymethyl cellulose (CMC) per styrene-butadiene rubber ( SBR) of 80- 98.5 per 0.5- 10 per 0.5- 5 per 0.5- 5 parts by weight, respectively.
  • the best negative electrode’ composition ratio is 94.5 per 1 per 2.25 per 2.25 parts by weight, respectively.
  • the most preferable negative electrode active material is artificial graphite for preparing the negative electrode according to the mentioned compositions.
  • the prepared electrolyte solution comprises 1 . 0 - 1 . 5 molars lithium hexafluorophosphate ( LiPFe) ; the solvent, which can be selected from any one of ethylene carbonate (EC), ethyl methyl carbonate (EMC) and dimethyl carbonate (DMC) or combination thereof; and the additive, which can be selected from any one of vinylene carbonate (VC) , fluoroethylene carbonate (FEC), propane sultone (PS), lithium difluorophosphate (LiPO2F2) and methylene methanedisulfonate (MMDS) or combination thereof in the total amount of 0.1- 12 percent by weight of electrolyte solution.
  • the solvent which can be selected from any one of ethylene carbonate (EC), ethyl methyl carbonate (EMC) and dimethyl carbonate (DMC) or combination thereof
  • the additive which can be selected from any one of vinylene carbonate (VC) , fluoroethylene carbonate (FEC), propane
  • the most preferable lithium hexafluorophosphate (LiPFe) concentration is 1.2 molars in a solvent mixture of ethylene carbonate (EC), ethyl methyl carbonate (EMC) and dimethyl carbonate (DMC) at the ratio of 5-30 per 5-40 per 30-90 parts by weight, where the best solvent ratio is 25 per 5 per 70 parts by weight.
  • Vinylene carbonate (VC) additive is used in the amount of 2 percent by weight of electrolyte solution, combined with the other above- mentioned additives in the amount of 0. 1- 10 percent by weight of electrolyte solution, where the most preferable additives consist of vinylene carbonate (VC) in the amount of 2 percent combined with fluoroethylene carbonate (FEC) in the amount of 0.1 percent by weight of electrolyte solution.
  • Lithium-ion button cells were prepared with positive electrode containing positive electrode active material in the form of NMC material as the core and carbon black as the shell (LiNMC@C or NMC @C) with production steps being:
  • the positive electrode for lithium-ion button cells was prepared. Materials comprising NMC material were mixed using mechanofusion for 1- 10 minutes, and then carbon black was added and stirred to mix for additional 1-60 minutes with ratios by weight of NMC material per carbon black of 98 per 2 and 99 per 1, respectively, yielding the positive electrode active material with NMC material core and carbon black shell.
  • the obtained positive electrode active material was mixed with carbon black that was conductive carbon, and polyvinylidene fluoride (PVDF) binder, at a ratio of 94 per 4 per 2 parts by weight.
  • NMC material used was NMC622 with addition of an organic solvent being N-methyl-2-pyrrolidone solution. 2.
  • Electrolyte solution was prepared, using 1.2 molars lithium hexafluorophosphate (LiPFe) in a solvent mixture with a ratio of ethylene carbonate (EC) per ethyl methyl carbonate (EMC) per dimethyl carbonate (DMC)of 25 per 5 per 70 parts by weight of electrolyte solution, respectively, and using two additives, namely vinylene carbonate (VC) and fluoroethylene carbonate (FEC) at 2 and 0.5 percent by weight of electrolyte solution, respectively.
  • LiPFe lithium hexafluorophosphate
  • EMC ethyl methyl carbonate
  • DMC dimethyl carbonate
  • Lithium-ion button cells were assembled, using the positive electrode and electrolyte solution prepared above.
  • the negative electrode used lithium and polymer film separator made from polyethylene.
  • CR2032 button cells were produced.
  • the prepared lithium- ion button cells were tested for their capacity where battery charge/discharge rates (C -rates) were controlled from 0.1C to 5.0C for 5 cycles each at 3.0-4.2 volts and 25 degree Celsius.
  • C -rates battery charge/discharge rates
  • the battery capacity with the positive electrode active material being NMC material without shell was found to be more decreased than that with electrode active materials being NMC material core and carbon black shell.
  • carbon black used as the shell in the amount of 1 percent or at a ratio by weight of NMC material per carbon black of 99 per 1 at a C rate of 0. 1C had higher capacity retention compared with materials with carbon black used as the shell at 2 percent or at a ratio by weight of NMC material per carbon black of 98 per 2 at the charge/discharge rate of batteries.
  • the charge capacity was found to be less decreased than when the amount of carbon black used as the shell was 1 percent or at a ratio by weight of NMC material per carbon black of 99 per 1 at C rates from 3C up.
  • NMC material core and carbon black shell used as the positive electrode active material for lithium-ion batteries helped enhance batteries’ performance, particularly upon using the positive electrode active material wherein NMC material per carbon black shell was 99 per 1 by weight at batteries’ charge/discharge rates of 0.L2.0C.
  • Example B Invention of Lithium-Ion Pouch Cells
  • the positive electrode for lithium- ion pouch cells was prepared, using the same compositions and process as in step 1 of Example A and a selected ratio by weight of NMC material per carbon black of 99 per 1 for positive electrode active material with NMC material core and carbon black shell; coated on aluminium foil; and then dried.
  • the negative electrode for lithium-ion pouch cells was prepared, using artificial graphite as an negative electrode active material by grinding artificial graphite using high energy ball mill; and then mixing with carbon black that was conductive carbon, and two binders, namely styrenebutadiene rubber (SBR) and carboxymethyl cellulose (CMC).
  • the prepared negative electrode had a ratio of artificial graphite per carbon black that was conductive carbon per styrene- butadiene rubber (SBR) per carboxymethyl cellulose (CMC) of 94.5 per 1 per 2.25 per 2.25, respectively.
  • organic solvent was added that could be selected from either ethanol or water or both, wherein this Example B used ethanol mixed with water at a ratio of 30 per 70 by volume, respectively. This was coated on copper foil, and then dried.
  • Electrolyte solution was prepared, using 1.2 molars lithium hexafluorophosphate (LiPFe) in a solvent mixture with a ratio of ethylene carbonate (EC) per ethyl methyl carbonate (EMC) per dimethyl carbonate (DMC)of 25 per 5 per 70 parts by weight of electrolyte solution, respectively; and using a combination of two additives consisting of the first one being vinylene carbonate (VC) at 2 percent by weight of electrolyte solution, and the second one that could be selected from any one of fluoroethylene carbonate (FEC) , propane sultone ( PS) and lithium difluorophosphate (LiPO2F2), methylene methanedisulfonate (MMDS) or combination thereof in the amount of 0.1-10 percent by weight of electrolyte solution.
  • LiPFe lithium hexafluorophosphate
  • VC vinylene carbonate
  • MMDS methylene methanedisulfonate
  • Lithium- ion pouch cells were assembled, using the prepared positive electrode in amounts of 17-23 milligrams per square centimetre, the prepared negative electrode in amounts of 10- 15 milligrams per square centimetre, the prepared electrolyte solution in amounts of 18-20 percent of cell weight and polymer film separator made from polyethylene, where the capacity of the prepared lithium-ion pouch cells was 200 milliampere-hour (mAh).
  • LiPFe lithium hexafluorophosphate
  • ECEMCDMC ethylene carbonate, ethyl methyl carbonate and dimethyl carbonate
  • VC vinylene carbonate

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Abstract

A lithium-ion battery with a positive electrode containing positive electrode active material being NMC material as the core and carbon black as the shell; an negative electrode containing negative electrode active material being graphite-type carbon, oxide material or lithium, depending on the form of the invented lithium-ion battery; and electrolyte solution used, consisting of lithium hexafluorophosphate (LiPF6) salt in solvent with vinylene carbonate (VC)-type additive combined with other additives comprising fluoroethylene carbonate (FEC), propane sultone (PS) and lithium difluorophosphate (LiPO2F2), methylene methanedisulfonate (MMDS), where additives help minimise gas formation in the lithium-ion battery during charge/discharge and maintain the battery's performance. Positive electrode preparation consists of mechanofusion, and the negative electrode is prepared by grinding the negative electrode active material using high energy ball mill, or lithium may be used as the negative electrode. Then the lithium-ion battery is formed that consists of the positive electrode active material, negative electrode active material and electrolyte solution prepared, combined with polymer film as a separator.

Description

LITHIUM ION BATTERY WITH POSITIVE ELECTRODE CONTAINING NMC MATERIAL AS THE CORE AND CARBON BLACK AS THE SHELL
Field of the Invention
Electrical and chemical engineering related to lithium-ion batteries with positive electrode containing NMC (nickel manganese cobalt) material as the core and carbon black as the shell Background of the Invention
A battery is an energy-retaining device capable of converting chemical energy to electrical power. Batteries can be divided into two types, namely primary batteries that are disposable and secondary batteries that are rechargeable. Popular secondary batteries at present are lithium-ion ones, which use lithium in the form of inorganic compounds capable of generating electrical power from lithium ions’ mobility.
Lithium-ion batteries are highly popular for electronic and portable electrical devices as well as in electrical vehicle industry. Lithium-ion batteries can be produced in several forms according to their use, such as button cells, cylindrical cells, pouch cells and prismatic cells. In addition, there are battery packs used for massive electrical power generation, such as those in electrical vehicles, etc.
A lithium-ion battery cell consists of a positive electrode, an negative electrode, electrolyte solution and a separator. The positive electrode contains positive electrode active material, which can absorb and emit lithium ions, made from a lithium-containing material, such as lithium cobalt oxide LiCoCh), which is the first positive electrode active material in positive electrode production for lithium-ion batteries, but its safety is found to be low; lithium manganese oxide (LiM CU) with high thermal stability, with safety but low cycle life; lithium iron phosphate (LiFePCU) with high safety, small size, high stability and high use cycles but lower energy density than that of other types of lithium batteries. In addition, there is Lithium Nickel Manganese Cobalt Oxide (NMC material, or LiNMC or NMC) containing nickel, manganese and cobalt with different element ratios. For example, NMC111 is LiNMC containing nickel per manganese per cobalt at 1 per 1 per 1, or NMC811 contains nickel per manganese per cobalt at 8 per 1 per 1. The LiNMC utilises good properties of nickel, manganese and cobalt. For example, nickel has high specific energy but low stability while manganese has low internal resistance. Combination of these elements provides the lithium material with strength and thermal stability, fit for use requiring high battery capacity and low heat generation rate like in electrical vehicles.
However, in order to enhance the positive electrode’ s electrical conductivity, positive electrode active material has been made from NMC material formed in a structure containing metal oxide as the core, with the shell (core-shell particle, core@shell), where the external shell helps increase energy from electrolyte- adsorbing surface and increase electrical conductivity that may affect batteries’ performance and useful life. Inventions have been disclosed in various patents. For example:
A Chinese patent application number CN108539193A has invented a positive electrode with positive electrode active material containing NMC material as the core and carbon nanotube as the shell with the proportion of carbon nanotube shell of 0.01 to 5% by weight of the NMC material core, where particle sizes of NMC material core are 5- 15 microns. The invented positive electrode has the electric charge of 2.5-4.5 V, the initial charge/ discharge rate greater than 240 mAh/g (milliampere-hour per gram) and the capacity retention ratio of 90 percent at 100 charge cycles.
A Chinese patent application number CN111354936A has produced a positive electrode containing NMC material as the core, and the shell of carbon containing nanosized magnesium oxide or aluminium oxide.
A Chinese patent application number CN112331830A has presented the invention of lithium-ion battery’s positive electrode in the form containing NMC material as the core, and the shell. The NMC material core can be selected from NMC 111, NMC532 or NMC811 , and graphene is used as the shell, where the ratio of NMC material core per the graphene shell is 1 per 0.005-0.1, and the ratio of NMC material core and graphene shell per acetylene black- type conductive material per polyvinylidene fluoride (PVDF)-type binder used is 80 per 10 per 10.
Based on the above information on lithium-ion batteries, it has been found that positive electrodes have diverse compositions and are an important variable affecting batteries’ performance and properties. Negative electrodes, the electrolyte solution and separators also are critical. Negative electrodes contain negative electrode active material being carbon, such as graphite or nanocarbon, or lithium- containing material. Negative electrode production may combine the negative electrode active material with conductive material and binder for enhancing the negative electrode’s performance.
The electrolyte solution contains lithium salts; generally popular ones of which are lithium hexafluorophosphate (LiPFe), lithium tetrafluoroborate (LiBF4), lithium bis(fluorosulfonyl) imide (LiFSI), etc. These lithium salts are dissolved in organic solution, such as ethylene carbonate (EC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), propylene carbonate (PC), etc. In addition, there are separators, which keep the positive electrode and negative electrode apart to avoid contact, generally being polymers, such as polyethylene (PE) , polypropylene (PP), etc. Invention related to lithium- ion batteries using positive electrodes, negative electrodes and electrolyte solution has been disclosed in various patents. For example:
A US patent application number US20210159541A1 has invented a battery with positive electrode using positive electrode active material being NMC111 material combined with conductive carbon and a polyvinylidene fluoride (PVDF)-type binder, and negative electrode using negative electrode active material being artificial graphite combined with styrene-butadiene rubber (SBR) and carboxymethyl cellulose (CMC). Electrolyte solution is used, where lithium salts are lithium hexafluorophosphate ( LiPFe) , lithium bis( fluoro sulfonyl) imide ( LiFSI) and lithium tetrafluoroborate (LiBEp at the ratio of 1 per 0.01- 1.2 per 0.05-0.7 by mole, respectively. Also, a solvent mixture of ethylene carbonate (EC), ethyl methyl carbonate (EMC) and dimethyl carbonate (DMC) is used. As are vinylene carbonate (VC), fluoroethylene carbonate (FEC) and propane sultone (PS) additives at 1-10 percent by weight of electrolyte solution.
A European patent application number EP39168504A4 has used an negative electrode active material being artificial graphite, and a US patent number US 11152621B2 has used negative electrode’ s retaining material being artificial graphite but with surface improvement by nitrogen atom addition. A US patent number US 10897062B2 has produced a battery with positive electrode containing NMC material; negative electrode containing graphite coated with amorphous carbon; lithium bis( fluoro sulfonyl) imide (LiFSI) and lithium hexafluorophosphate (LiPFe) electrolyte solution in a solvent mixture of ethylene carbonate (EC), ethyl methyl carbonate (EMC) and dimethyl carbonate (DMC); and a lithium difluorophosphate (LiPO2F2) additive.
In addition, there was a research journal with related invention, namely the Energy Storage Materials journal with a research entitled ‘Core-shell Ni-rich NMC- nanocarbon positive electrode from scalable solvent- free mechanofusion for high-performance 18650 Li- ion batteries’ that produced positive electrode active material in the form of a structure containing NMC material as the core using NMC811 material, and the nanocarbon shell, with a ratio of NMC material per nanocarbon of 90 per 10 percent by weight, respectively. The nanocarbon used was carbon black type passing through mechanofusion for forming a structure containing the NMC material as the core and the nanocarbon as the shell. In addition, carbon black was used as a conductive material, and polyvinylidene fluoride (PVDF) was used as a binder for making the positive electrode of batteries. The batteries were produced as 18650 cylindrical cells, using a ratio of NMC material as the core with nanocarbon as the shell per carbon black as the conductive material per poly vinylidene fluoride (PVDF) of 946 per 24 per 3 by weight, respectively. The electrolyte solution was used that contained 10 molar lithium hexafluorophosphate (LiPFe) in solvents of ethylene carbonate (EC) combined with dimethyl carbonate (DMC) at a ratio of 1 per 1 by volume, respectively. The negative electrode was used that consisted of graphite-type negative electrode active material, carbon black as a conductive material and poly vinylidene fluoride (PVDF) as a binder at a ratio of 96.6 per 1.7 per 1.7 by weight, respectively. In addition, button cells were invented, using lithium as the negative electrode, with the positive electrode containing NMC material as the core and nanocarbon as the shell per carbon black as the conductive material per poly vinylidene fluoride at 80 per 10 per 10 by weight, respectively.
Apart from foreign patents as referred to above, there are patents disclosing invention in terms of lithium-ion batteries that were applied for in Thailand. For example:
A Thai patent application number 1601000751 has invented a positive electrode of lithium sulfur battery in the form of structure containing the core and shell, using sulfur as the core and nanocarbon as the shell at a ratio of 95 per 5 by weight, respectively, and using mechanofusion for forming materials into the core and shell structure with a ratio of positive electrode containing sulfide with nanocarbon as the shell per nanocarbon- type conductive material per poly vinylidene fluoride (PVDF)-type binder of 6 per 3 per 1 by weight, respectively.
A thai patent application number 1601000853 has invented an electrode, consisting of NMC material as positive electrode active material with a ratio of positive electrode active material per nanocarbon-type conductor per polyvinylidene fluoride (PVDF)-type binder of 8 per 1 per 1 by weight, respectively. A Thai patent application number TH 1601001280 has invented lithium-ion battery's positive electrode in the form of structure having a core and a shell, using lithium polysulfide as the core and nanocarbon as the shell at a ratio of 95 per 5 by weight, respectively, and a ratio of positive electrode consisting of lithium sulfide with nanocarbon as the shell per nanocarbon- type conductive material per poly vinylidene fluoride (PVDF)-type binder at 6 per 3 per 1 by weight, respectively.
A Thai patent application number 1801007531 has invented a positive electrode of lithium- ion battery in a form with positive electrode active material containing lithium nickel aluminium oxide as the core and nanocarbon as the shell at the ratio of 70-95 per 5-30 by weight, respectively.
A Thai patent application number 1801005876 has presented a manufacturing process for lithium-ion battery’s electrode, where positive electrode contains lithium metal silicate mixed with carbon-type conductor and binder, such as polyvinylidene fluoride (PVDF). The obtained mixture is coated on aluminium foil, and the obtained lithium-ion battery has initial electrical discharge of 1,950 mAh/g at a battery discharge rate (C rate) of 0.05.
A Thai patent application number 1501005436 has invented an negative electrode, using negative electrode active material being silicon, graphene as a conductor and polyacrylic acid as a binder at the ratio of 15-85 per 3-75 per 3-60 by weight, respectively.
Although many lithium-ion batteries and components thereof have been invented, lithium- ion battery development for improved performance - increase in capacity, thermal stability, weight as well as safety - is still required in the industry. Accordingly, in order to enhance lithium-ion batteries’ performance, this invention has developed a positive electrode with positive electrode active material containing NMC material core and carbon black shell, improved electrolyte solution for the enhanced performance, using additive that helps minimise undesirable reactions that may produce gases in the system and affect the useful life, and also optimised negative electrode compositions of battery.
Summary of the Invention
To produce a high-performance lithium- ion battery, focusing on improvement of the positive electrode, using positive electrode active material in the form of core- shell particle. The core uses NMC material (LiNMC or NMC), and carbon black is used as the shell, where the positive electrode uses the ratio of NMC material as the core per carbon black as the shell ranging from 95.01 per 4.99 to 99.5 per 0.5 parts by weight. Also, electrolyte solution is provided such that it has a property to minimise gas pores with use of additive. This invention is related to a lithium-ion battery-preparing method, wherein it comprises steps:
A. Mixing of materials used in making the positive electrode containing positive electrode active material, conductor and binder, where the positive electrode active material is in the form of core-shell particle, using the core being NMC material and using carbon black as the shell. The prepared positive electrode is coated on aluminium foil.
B. Mixing of materials used in making the negative electrode containing an negative electrode active material, and probably conductor, and binder; as well as coating of the prepared negative electrode on copper foil, depending on the type of negative electrode
C. Preparation of electrolyte solution comprising lithium salt, solvent and additive
D. Assembling of lithium-ion battery using the positive electrode prepared from step A, the negative electrode prepared from step B, polymer film as a separator and electrolyte solution as a conductor for ions prepared from step C
Brief Description of the Drawings
Figure 1. Button cells’ capacity at various battery charge/discharge rates (C rates).
Figure 2. The capacity retention (percentage) upon use of pouch cells with use of 2% vinylene carbonate ( VC) and 0- 10% fluoroethylene carbonate ( FEC) additives by weight of electrolyte solution.
Figure 3. The capacity retention (percentage) upon use of pouch cells with use of 2% vinylene carbonate (VC) and 0.1% fluoroethylene carbonate (FEC) additives by weight of electrolyte solution at battery charge/discharge rates (C -rates) of 0.5C and 1.0C.
Detailed Description of the Invention
This invention discloses the lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell and the manufacturing process of the said battery as follows.
The positive electrode contains the positive electrode active material, which can absorb and emit lithium ions, made from a lithium- containing material in the form of core- shell particle (core@ shell), where the metal oxide core is Lithium Nickel Manganese Cobalt Oxide (NMC material or LiNMC or NMC) and the shell is carbon black with the ratio of NMC material as the core per carbon black as the shell ranging from 95.01 per 4.99 to 99.5 per 0.5 parts by weight, respectively. The preferred ratio ranges from 98 per 2 to 99 per 1 parts by weight, respectively. The most preferable ratio is 99 per 1 parts by weight, respectively. In addition, the positive electrode further comprises carbon as conductive material, and binder used for positive electrode, which has composition ratio of NMC material core and carbon black shell (NMC@C)per carbon used as the conductive material per the binder of 80-99 per 0.5-10 per 0.5-10 parts by weight, respectively. The best composition ratio of NMC material core and carbon black shell (NMC@C) per carbon used as the conductive material per the binder is 94 per 4 per 2 parts by weight, respectively.
Carbon used as the conductive material can be selected from any one of carbon black, nanocarbon, graphite or combination thereof, where the best carbon used as the conductive material is carbon black. The binder for the positive electrode can be selected from any one of polyvinylidene fluoride ( PVDF) , carboxymethyl cellulose ( CMC) , sodium carboxymethyl cellulose, butadiene rubber, styrene- butadiene rubber ( SBR) , poly( vinyl alcohol) ( PVA) or polyacrylic acid or combination thereof, where the most preferable binder for the positive electrode is polyvinylidene fluoride (PVDF).
The negative electrode contains any one of graphite-type carbon, oxide material or lithium or combination thereof to form the negative electrode active material, depending on the form of invented lithium-ion battery, where the preparation of negative electrode from either graphite-type carbon or oxide material or both comprises carbon as the conductive material, and binder used for negative electrode. The most preferable graphite-type carbon is artificial graphite. Carbon used as the conductive material can be selected from any one of carbon black, nanocarbon, graphite or combination thereof, where the best carbon used as the conductive material is carbon black. The binder for the negative electrode can be selected from any one of polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC) , sodium carboxymethyl cellulose, butadiene rubber, styrenebutadiene rubber (SBR), poly(vinyl alcohol) (PVA) or polyacrylic acid or combination thereof, where the most preferable binder for the negative electrode is either carboxymethyl cellulose (CMC) or styrene-butadiene rubber (SBR) or both.
The negative electrode has composition ratio of negative electrode active material being graphite- type carbon or oxide material per carbon used as the conductive material per carboxymethyl cellulose (CMC) per styrene-butadiene rubber (SBR) at 80-98.5 per 0.5-10 per 0.5-5 per 0.5-5 parts by weight, respectively. The best composition ratio is 94.5 per 1 per 2.25 per 2.25 parts by weight, respectively. The most preferable negative electrode active material is artificial graphite for preparing the negative electrode according to the mentioned compositions.
The electrolyte solution comprises a lithium salt and solvent, where:
A. The lithium salt is lithium hexafluorophosphate (LiPFe)in a concentration range of 1.0- 1.5 molars; the most preferable of which is 1.2 molars.
B. The solvent can be selected from any one of ethylene carbonate (EC), ethyl methyl carbonate (EMC) and dimethyl carbonate (DMC) or combination thereof, where the solvent ratio comprises ethylene carbonate (EC) per ethyl methyl carbonate (EMC) per dimethyl carbonate (DMC) at 5-30 per 5-40 per 30-90 parts by weight, and the best solvent ratio is 25 per 5 per 70 parts by weight, respectively.
C. The additive can be selected from any one of vinylene carbonate (VC), fluoroethylene carbonate ( FEC) , propane sultone ( PS) , lithium difluorophosphate ( LiPO2F2) , methylene methanedisulfonate (MMDS) or combination thereof in the amount of 0.1-12 percent by weight of electrolyte solution, where preferred additives comprise vinylene carbonate (VC) in the amount of 2 percent by weight of electrolyte solution, combined with any one of fluoroethylene carbonate ( FEC) , propane sultone ( PS) , lithium difluorophosphate LiPO2F2) , or methylene methanedisulfonate (MMDS) additives or combination thereof in the amount of 0.1- 10 percent by weight of electrolyte solution. The most preferable additive amounts comprise vinylene carbonate (VC) at 2 percent combined with fluoroethylene carbonate (FEC) at 0.1 percent by weight of electrolyte solution.
As above-mentioned, the most preferable electrolyte solution comprises 1.2 molars lithium hexafluorophosphate in ethylene carbonate (EC) per ethyl methyl carbonate (EMC) per dimethyl carbonate (DMC) solvents at 25 per 5 per 70 parts by weight, respectively, and vinylene carbonate (VC) and fluoroethylene carbonate (FEC) additives in the amounts of 2 and 0. 1 percent by weight of electrolyte solution, respectively.
The preparation of lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell comprises the following steps.
A. Prepare the positive electrode by making positive electrode active material from mixing lithium manganese cobalt oxide (NMC) as the core and carbon black as the shell using mechanofusion, wherein this method has small particles compressed and adhered to one another because of the introduced energy; then mixing the said positive electrode active material with carbon used as conductive material, and binder; then coating the prepared positive electrode on aluminium foil; and then drying.
B. Prepare the negative electrode that can be performed in two processes, depending on the negative electrode active material, wherein:
The first process, upon using the negative electrode active material being either graphite- type carbon or oxide material or both, contains a step of grinding graphite-type carbon or oxide material using high energy ball mill. Afterwards, add carbon used as the conductive material, binder and organic solvent, wherein the organic solvent can be selected from any one of N-methyl-2-pyrrolidone, ethanol or water or combination thereof; then coat the prepared negative electrode on copper foil; and then dry.
The second process uses the negative electrode containing the negative electrode active material being lithium metal in the form of lithium metal sheet.
C. Prepare the electrolyte solution comprising lithium hexafluorophosphate (LiPFe) salt, solvent and additive.
D. Assemble the lithium-ion battery using the positive electrode prepared from step A, the negative electrode prepared from step B, polymer film as a separator and the electrolyte solution as the ions transport as prepared from step C.
From A and B, the positive electrode prepared and coated on aluminium foil has a weight range of 17-23 milligrams per square centimetre and a thickness range of 110-250 micrometres. The negative electrode upon using the negative electrode active material being graphite- type carbon or oxide material as prepared and coated on the copper foil has a weight range of 10- 15 milligrams per square centimetre and a thickness range of 100-250 micrometres.
From A in the step of making the positive electrode active material, wherein the positive electrode contains the positive electrode active material in the form of core- shell particle ( core @ shell) being NMC material (LiNMC or NMC) as the metal oxide core with carbon black shell (NMC@C) where the ratio of materials containing NMC material as the core per carbon black as the shell ranges from 95.01 per 4.99 to 99.5 per 0.5 parts by weight, respectively, the preferred ratio ranges from 98 per 2 to 99 per 1 parts by weight, respectively. The most preferable ratio is 99 per 1 parts by weight, respectively. Also, the positive electrode has the ratio of NMC material core and carbon black shell per carbon used as the conductive material per the binder at 80-99 per 0.5- 10 per 0.5- 10 parts by weight, respectively. The best positive electrode’ s ratio is 94 per 4 per 2 parts by weight, respectively. Carbon used as the conductive material can be selected from any one of carbon black, nanocarbon or graphite or combination thereof, where the best carbon used as the conductive material is carbon black. The binder for the positive electrode can be selected from polyvinylidene fluoride ( PVDF) , carboxymethyl cellulose ( CMC) , sodium carboxymethyl cellulose, butadiene rubber, styrene-butadiene rubber, polycvinyl alcohol) (PVA) or polyacrylic acid or combination thereof, where the most preferable binder for the positive electrode is polyvinylidene fluoride (PVDF).
From B, the first process’ negative electrode- preparing step upon using the negative electrode active material being either graphite- type carbon or oxide material or both comprises carbon used as the conductive material, and the binder used for the negative electrode. The most preferable negative electrode active material of graphite-type carbon is artificial graphite; carbon used as the conductive material can be selected from any one of carbon black, nanocarbon, graphite or combination thereof, where the best carbon used as the conductive material is carbon black; and the binder for the negative electrode can be selected from any one of polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC), sodium carboxymethyl cellulose, butadiene rubber, styrene-butadiene rubber (SBR), poly(vinyl alcohol) (PVA) or polyacrylic acid or combination thereof, where the most preferable binder for the negative electrode is either carboxymethyl cellulose (CMC) or styrene-butadiene rubber (SBR) or both. The negative electrode has the preferred composition ratio comprising the negative electrode active material of graphite-type carbon or oxide material per carbon used as the conductive material per carboxymethyl cellulose (CMC) per styrene-butadiene rubber ( SBR) of 80- 98.5 per 0.5- 10 per 0.5- 5 per 0.5- 5 parts by weight, respectively. The best negative electrode’ composition ratio is 94.5 per 1 per 2.25 per 2.25 parts by weight, respectively. The most preferable negative electrode active material is artificial graphite for preparing the negative electrode according to the mentioned compositions.
From C, the prepared electrolyte solution comprises 1 . 0 - 1 . 5 molars lithium hexafluorophosphate ( LiPFe) ; the solvent, which can be selected from any one of ethylene carbonate (EC), ethyl methyl carbonate (EMC) and dimethyl carbonate (DMC) or combination thereof; and the additive, which can be selected from any one of vinylene carbonate (VC) , fluoroethylene carbonate (FEC), propane sultone (PS), lithium difluorophosphate (LiPO2F2) and methylene methanedisulfonate (MMDS) or combination thereof in the total amount of 0.1- 12 percent by weight of electrolyte solution. The most preferable lithium hexafluorophosphate (LiPFe) concentration is 1.2 molars in a solvent mixture of ethylene carbonate (EC), ethyl methyl carbonate (EMC) and dimethyl carbonate (DMC) at the ratio of 5-30 per 5-40 per 30-90 parts by weight, where the best solvent ratio is 25 per 5 per 70 parts by weight. Vinylene carbonate (VC) additive is used in the amount of 2 percent by weight of electrolyte solution, combined with the other above- mentioned additives in the amount of 0. 1- 10 percent by weight of electrolyte solution, where the most preferable additives consist of vinylene carbonate (VC) in the amount of 2 percent combined with fluoroethylene carbonate (FEC) in the amount of 0.1 percent by weight of electrolyte solution.
The followings are preparation examples of lithium-ion batteries with positive electrode containing NMC material as the core and carbon black as the shell, and such prepared batteries’ performance tests with reference to samples. This invention is, however, not limited to these examples.
Example A: Invention of Lithium-Ion Button Cells
Lithium-ion button cells were prepared with positive electrode containing positive electrode active material in the form of NMC material as the core and carbon black as the shell (LiNMC@C or NMC @C) with production steps being:
1. The positive electrode for lithium-ion button cells was prepared. Materials comprising NMC material were mixed using mechanofusion for 1- 10 minutes, and then carbon black was added and stirred to mix for additional 1-60 minutes with ratios by weight of NMC material per carbon black of 98 per 2 and 99 per 1, respectively, yielding the positive electrode active material with NMC material core and carbon black shell. The obtained positive electrode active material was mixed with carbon black that was conductive carbon, and polyvinylidene fluoride (PVDF) binder, at a ratio of 94 per 4 per 2 parts by weight. NMC material used was NMC622 with addition of an organic solvent being N-methyl-2-pyrrolidone solution. 2. Electrolyte solution was prepared, using 1.2 molars lithium hexafluorophosphate (LiPFe) in a solvent mixture with a ratio of ethylene carbonate (EC) per ethyl methyl carbonate (EMC) per dimethyl carbonate (DMC)of 25 per 5 per 70 parts by weight of electrolyte solution, respectively, and using two additives, namely vinylene carbonate (VC) and fluoroethylene carbonate (FEC) at 2 and 0.5 percent by weight of electrolyte solution, respectively.
3. Lithium-ion button cells were assembled, using the positive electrode and electrolyte solution prepared above. The negative electrode used lithium and polymer film separator made from polyethylene. CR2032 button cells were produced.
The prepared lithium- ion button cells were tested for their capacity where battery charge/discharge rates (C -rates) were controlled from 0.1C to 5.0C for 5 cycles each at 3.0-4.2 volts and 25 degree Celsius. According to Figure 1, the battery capacity with the positive electrode active material being NMC material without shell was found to be more decreased than that with electrode active materials being NMC material core and carbon black shell. Also, it was found that carbon black used as the shell in the amount of 1 percent or at a ratio by weight of NMC material per carbon black of 99 per 1 at a C rate of 0. 1C had higher capacity retention compared with materials with carbon black used as the shell at 2 percent or at a ratio by weight of NMC material per carbon black of 98 per 2 at the charge/discharge rate of batteries.
Upon increasing the amount of carbon black used as the shell to 2 percent or at a ratio by weight of NMC material per carbon black of 98 per 2, the charge capacity was found to be less decreased than when the amount of carbon black used as the shell was 1 percent or at a ratio by weight of NMC material per carbon black of 99 per 1 at C rates from 3C up.
Based on the test in this example, therefore, it was shown that NMC material core and carbon black shell used as the positive electrode active material for lithium-ion batteries helped enhance batteries’ performance, particularly upon using the positive electrode active material wherein NMC material per carbon black shell was 99 per 1 by weight at batteries’ charge/discharge rates of 0.L2.0C.
Example B: Invention of Lithium-Ion Pouch Cells
1. The positive electrode for lithium- ion pouch cells was prepared, using the same compositions and process as in step 1 of Example A and a selected ratio by weight of NMC material per carbon black of 99 per 1 for positive electrode active material with NMC material core and carbon black shell; coated on aluminium foil; and then dried.
2. The negative electrode for lithium-ion pouch cells was prepared, using artificial graphite as an negative electrode active material by grinding artificial graphite using high energy ball mill; and then mixing with carbon black that was conductive carbon, and two binders, namely styrenebutadiene rubber (SBR) and carboxymethyl cellulose (CMC). The prepared negative electrode had a ratio of artificial graphite per carbon black that was conductive carbon per styrene- butadiene rubber (SBR) per carboxymethyl cellulose (CMC) of 94.5 per 1 per 2.25 per 2.25, respectively. In addition, organic solvent was added that could be selected from either ethanol or water or both, wherein this Example B used ethanol mixed with water at a ratio of 30 per 70 by volume, respectively. This was coated on copper foil, and then dried.
3. Electrolyte solution was prepared, using 1.2 molars lithium hexafluorophosphate (LiPFe) in a solvent mixture with a ratio of ethylene carbonate (EC) per ethyl methyl carbonate (EMC) per dimethyl carbonate (DMC)of 25 per 5 per 70 parts by weight of electrolyte solution, respectively; and using a combination of two additives consisting of the first one being vinylene carbonate (VC) at 2 percent by weight of electrolyte solution, and the second one that could be selected from any one of fluoroethylene carbonate (FEC) , propane sultone ( PS) and lithium difluorophosphate (LiPO2F2), methylene methanedisulfonate (MMDS) or combination thereof in the amount of 0.1-10 percent by weight of electrolyte solution.
4. Lithium- ion pouch cells were assembled, using the prepared positive electrode in amounts of 17-23 milligrams per square centimetre, the prepared negative electrode in amounts of 10- 15 milligrams per square centimetre, the prepared electrolyte solution in amounts of 18-20 percent of cell weight and polymer film separator made from polyethylene, where the capacity of the prepared lithium-ion pouch cells was 200 milliampere-hour (mAh).
From the prepared lithium-ion pouch cells using the combination of two additives (where the first one was vinylene carbonate (VC); the use of the second one helping to minimise gas formation in the electrolyte solution during charge/discharge and serving to minimise potential reactions in the system was tested and studied at 2.7-4.2 volts and 25 degrees Celsius; and batteries’ charge/discharge rate (C rate) was controlled at 1.0C as shown in Table 1, upon using the second additive in the amount of 1 percent by weight of electrolyte solution combined with the first additive at 2 percent by weight of electrolyte solution, it was found that the use of the second additive being propane sultone (PS) combined with the first additive being vinylene carbonate (VC) helped minimise formed gas the best. In addition, when comparing amounts of the second additive being fluoroethylene carbonate (FEC) used at 0.1, 1.0 and 10 percent by weight of electrolyte solution, it was found that the higher amount of fluoroethylene carbonate (FEC), the less gas was formed in the electrolyte solution as demonstrated in Table 1.
Table 1. Types and amounts of the 2nd additive used in 1.2 molars lithium hexafluorophosphate (LiPFe) electrolyte solution in the solvent mixture of ethylene carbonate, ethyl methyl carbonate and dimethyl carbonate (ECEMCDMC) at a ratio of 25 per 5 per 70 parts by weight, respectively, with the 1st additive being vinylene carbonate (VC) at 2 percent by weight of electrolyte solution.
Figure imgf000016_0001
However, upon testing battery capacity performance when using the second additive being fluoroethylene carbonate (FEC) in amounts of 0.1, 1.0 and 10 percent by weight of electrolyte solution, combined with the first additive being vinylene carbonate (VC) at 2 percent by weight of electrolyte solution with a batteries’ charge/discharge rate (C rate) controlled at 0.5C as per Figure 2, it was found that when the number of cycles were higher, the battery capacity was rapidly decreased when fluoroethylene carbonate (FEC) was used at 1.0 and 10 percent by weight of electrolyte solution, compared to when not using fluoroethylene carbonate (FEC). The battery capacity when using fluoroethylene carbonate (FEC) at 0.1 percent by weight of electrolyte solution was, however, found to be least decreased when compared with use of fluoroethylene carbonate (FEC) at 1.0 and 10 percent by weight of electrolyte solution and better than use of vinylene carbonate (VC) alone. In addition, Figure 3 tested charge/discharge rates (C-rates) at 0.5C and 1.0C of batteries using additives being vinylene carbonate ( VC) at 2 percent combined with fluoroethylene carbonate (FEC) at 0. 1 percent by weight of electrolyte solution. It was found that with 400 charge/discharge use cycles, batteries still had the capacity greater than 90 percent of the original capacity.
Based on the test prepared above, it was found that each additive not only helped minimise gas formation in the electrolyte solution but also affected batteries’ other performance aspects, such as charge/discharge, conductivity, stability for use, etc. Optimal additive types and amounts, therefore, led to optimised batteries’ performance. It has been found that lithium-ion pouch cells using compositions of positive electrode and negative electrode provided above and electrolyte solution using additives being vinylene carbonate (VC) combined with fluoroethylene carbonate (FEC) at 2 and 0. 1 percent by weight of electrolyte solution, respectively, will be lithium-ion batteries with the best performance.
Best Mode of the Invention
As described in Detailed Description of the Invention

Claims

Claims
1. A lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell, wherein the lithium-ion battery comprises a positive electrode, an negative electrode, a polymer film as an electrode separator and an electrolyte solution.
The positive electrode contains positive electrode active material in the form of metal oxide core, and shell (core@ shell); that is, NMC material (LiNMC or NMC) as the metal oxide core and carbon black as the shell (NMC@C), where the ratio of NMC material (LiNMC or NMC) as the core per carbon black as the shell is in a range of 95.01 per 4.99 to 99.5 per 0.5 parts by weight.
The positive electrode further comprises carbon as conductive material, and binder.
2. The lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to claim 1, wherein the negative electrode contains negative electrode active material that can be selected from any one of graphite-type carbon, oxide material or lithium or combination thereof, wherein the negative electrode using the negative electrode active material from either graphite-type carbon or oxide material or both contains carbon as conductive material, and binder.
3. The lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to claim 1 or 2, wherein the most preferable negative electrode active material is graphite-type carbon.
4. The lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to either claim 2 or 3, wherein the most preferable negative electrode active material of graphite-type carbon is artificial graphite.
5. The lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to any one of claims 1 to 4, wherein carbon used as the conductive material can be selected from any one of carbon black, nanocarbon or graphite or combination thereof.
6. The lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to any one of claim 1 or 2 or 5, wherein the most preferable carbon used as the conductive material is carbon black.
7. The lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to either claim 1 or 2, wherein the binder used for the positive electrode and negative electrode can be selected from any one of polyvinylidene fluoride ( PVDF) , carboxymethyl cellulose (CMC) , sodium carboxymethyl cellulose, butadiene rubber, styrenebutadiene rubber (SBR), poly(vinyl alcohol) (PV A) or polyacrylic acid or combination thereof.
8. The lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to either claim 1 or 7, wherein the most preferable binder for using with the positive electrode is polyvinylidene fluoride (PVDF).
9. The lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to claim 1, wherein the positive electrode active material has the preferred ratio of NMC material (LiNMC or NMC) as the core per carbon black as the shell in a range of 98 per 2 to 99 per 1 parts by weight.
10. The lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to either claim 1 or 9, wherein the positive electrode active material has the most preferable ratio of NMC material (LiNMC or NMC) as the core per carbon black as the shell of 99 per 1 parts by weight.
11. The lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to any one of claims 1 or 5 to 10, wherein the positive electrode has the ratio of NMC material core and carbon black shell (NMC @ C) per carbon used as the conductive material per the binder of 80-99 per 0.5-10 per 0.5-10 parts by weight, respectively.
12. The lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to any one of claims 1 or 5 to 11, wherein the positive electrode has the best ratio of NMC material core and carbon black shell (NMC@C) per carbon used as the conductive material per the binder of 94 per 4 per 2 parts by weight, respectively.
13. The lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to any one of claims 1 to 7, wherein the most preferable binder for using with the negative electrode is either carboxymethyl cellulose (CMC) or styrene- butadiene rubber (SBR) or both.
14. The lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to any one of claims 1 to 7 or 13, wherein the negative electrode has the ratio of negative electrode active material compositions being graphite-type carbon or oxide material per carbon as the conductive material per carboxymethyl cellulose (CMC) per styrenebutadiene rubber (SBR) of 80-98.5 per 0.5-10 per 0.5-5 per 0.5-5 parts by weight, respectively.
15. The lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to any one of claims 1 to 7 or 13 to 14, wherein the negative electrode has the best ratio of negative electrode active material compositions being graphite-type carbon or oxide material per carbon as the conductive material per carboxymethyl cellulose (CMC) per styrene-butadiene rubber (SBR) of 94.5 per 1 per 2.25 per 2.25 parts by weight, respectively.
16. The lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to claim 1, wherein the electrolyte solution comprises a lithium salt, solvent and additive, where:
A. The lithium salt is lithium hexafluorophosphate (LiPFe) in a concentration range of 1.0 - 1.5 molars.
B. The solvent can be selected from any one of ethylene carbonate (EC), ethyl methyl carbonate (EMC) and dimethyl carbonate (DMC) or combination thereof.
C. The additive can be selected from any one of vinylene carbonate (VC), fluoroethylene carbonate ( FEC) , propane sultone ( PS) , lithium difluorophosphate ( LiPO2F2) , methylene methanedisulfonate (MMDS) or combination thereof in the amount of 0.1-12 percent by weight of electrolyte solution.
17. The lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to claim 16, wherein solvents have the ratio of ethylene carbonate (EC) per ethyl methyl carbonate (EMC) per dimethyl carbonate (DMC) of 5-30 per 5-40 per 30-90 parts by weight, respectively.
18. The lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to any one of claims 16 to 17, wherein solvents have the best ratio of ethylene carbonate (EC) per ethyl methyl carbonate (EMC) per dimethyl carbonate (DMC) of 25 per 5 per 70 parts by weight, respectively.
19. The lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to claim 16, wherein preferred additives comprise vinylene carbonate (VC) in the amount of 2 percent by weight of electrolyte solution combined with any one of fluoroethylene carbonate (FEC), propane sultone (PS), lithium difluorophosphate (LiPO2F2) , methylene methanedisulfonate (MMDS) additives or combination thereof in the amount of 0. 1-10 percent by weight of electrolyte solution.
20. The lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to either claim 16 or 19, wherein the most preferable additives comprise vinylene carbonate (VC) and fluoroethylene carbonate (FEC) in amounts of 2 and 0. 1 percent by weight of electrolyte solution, respectively.
21. The lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to either claim 1 or 16, wherein the most preferable electrolyte solution comprises lithium hexafluorophosphate at a concentration of 1.2 molars in ethylene carbonate (EC) per ethyl methyl carbonate (EMC) per dimethyl carbonate (DMC) solvents at 25 per 5 per 70 parts by weight, respectively, and vinylene carbonate (VC) and fluoroethylene carbonate (FEC) additives in amounts of 2 and 0.1 percent by weight of electrolyte solution, respectively.
22. A preparing method of lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell, comprising:
A. Prepare the positive electrode by making positive electrode active material from mixing NMC material as the core and carbon black as the shell using mechanofusion. Mix the said positive electrode active material with carbon used as conductive material, and binder; then coat the prepared positive electrode on aluminium foil; and dry.
B. Prepare the negative electrode.
C. Prepare electrolyte solution comprising lithium hexafluorophosphate ( LiPFe) salt, solvent and additive.
D. Assemble the lithium-ion battery using the positive electrode prepared from step A, the negative electrode prepared from step B, a polymer film as an electrode separator and the electrolyte solution as an ion conductor as prepared from step C.
Step B to prepare the negative electrode can be performed using two processes, depending on negative electrode active material, wherein:
The first process, wherein the negative electrode uses the negative electrode active material being either graphite-type carbon or oxide material or both, has steps of grinding graphitetype carbon or oxide material using high energy ball mill; then adding carbon used as conductive material, binder and organic solvent, wherein the organic solvent can be selected from any one of N- methyl- 2- pyrrolidone, ethanol or water or combination thereof; then coating the prepared negative electrode on copper foil; and thendrying. The second process uses the negative electrode with the negative electrode active material being lithium metal in the form of lithium metal sheet.
23. The preparing method of lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to claim 22, wherein the preferred negative electrode active material is graphite-type carbon.
24. The preparing method of lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to claim 22 or 23, wherein the most preferable negative electrode active material of graphite-type carbon is artificial graphite.
25. The preparing method of lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to claim 22, wherein the positive electrode contains the positive electrode active material in the form of metal oxide core, and shell (core@ shell); that is, NMC material (LiNMC or NMC) as the metal oxide core and carbon black as the shell (NMC @C), where the ratio of NMC material (LiNMC or NMC) as the core per carbon black as the shell is in a range of 95.01 per 4.99 to 99.5 per 0.5 parts by weight. The positive electrode further comprises carbon used as the conductive material, and the binder.
26. The preparing method of lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to claim 22 or 25, wherein carbon used as the conductive material can be selected from any one of carbon black, nanocarbon, graphite or combination thereof.
27. The preparing method of lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to any one of claims 22 or 25 to 26, wherein the best carbon used as the conductive material is carbon black.
28. The preparing method of lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to claim 22 or 25, wherein the binder for the positive electrode and negative electrode can be selected from any one of polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC), sodium carboxymethyl cellulose or butadiene rubber, styrene- butadiene rubber (SBR), poly(vinyl alcohol) (PVA) or polyacrylic acid or combination thereof.
29. The preparing method of lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to any one of claim 22 or 25 or 28, wherein the most preferable binder for using with the positive electrode is polyvinylidene fluoride (PVDF).
30. The preparing method of lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to claim 22 or 25, wherein the positive electrode active material has the preferred ratio of NMC material (LiNMC or NMC) as the core per carbon black as the shell in a range of 98 per 2 to 99 per 1 parts by weight.
31. The preparing method of lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to claim 22 or 25 or 30, wherein the positive electrode active material has the most preferable ratio of NMC material (LiNMC or NMC) as the core per carbon black as the shell of 99 per 1 parts by weight.
32. The preparing method of lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to any one of claims 22 or 25 or 30 to 31, wherein the positive electrode has the ratio of NMC material core and carbon black shell (NMC@C)per carbon used as the conductive material per the binder of 80-99 per 0.5-10 per 0.5-10 parts by weight, respectively.
33. The preparing method of lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to any one of claims 22 or 25 or 30 to 32, wherein the positive electrode has the best composition ratio of NMC material core and carbon black shell (NMC@C) per carbon used as the conductive material per the binder of 94 per 4 per 2 parts by weight, respectively.
34. The preparing method of lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to any one of claims 22 or 25 or 28 to 29 or 32 to 33, wherein the most preferable binder for using with the negative electrode is either carboxymethyl cellulose (CMC) or styrene-butadiene rubber (SBR) or both.
35. The preparing method of lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to any one of claims 22 to 24 or 34, wherein the negative electrode has the ratio of negative electrode active material composition being graphite- type carbon or oxide material per carbon used as the conductive material per carboxymethyl cellulose (CMC) per styrene-butadiene rubber (SBR) of 80-98.5 per 0.5-10 per 0.5-5 per 0.5-5 parts by weight, respectively.
36. The preparing method of lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to any one of claims 22 to 24 or 35, wherein the negative electrode has the best composition ratio of negative electrode active material being graphite- type carbon or oxide material per carbon used as the conductive material per carboxymethyl cellulose (CMC) per styrene-butadiene rubber (SBR)of 94.5 per 1 per 2.25 per 2.25 parts by weight, respectively.
37. The preparing method of lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to claim 22, wherein the electrolyte solution comprises a lithium salt, solvent and additive, where:
A. The lithium salt is lithium hexafluorophosphate (LiPFe) in a concentration range of 1.0- 1.5 molars.
B. The solvent can be selected from any one of ethylene carbonate (EC), ethyl methyl carbonate (EMC) and dimethyl carbonate (DMC) or combination thereof.
C. The additive can be selected from any one of vinylene carbonate (VC), fluoroethylene carbonate ( FEC) , propane sultone ( PS) , lithium difluorophosphate ( LiPO2F2) , methylene methanedisulfonate (MMDS) or combination thereof in the amount of 0.1-12 percent by weight of electrolyte solution.
38. The preparing method of lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to either claim 22 or 37, wherein solvents have the ratio of ethylene carbonate (EC) per ethyl methyl carbonate (EMC) per dimethyl carbonate (DMC) of 5-30 per 5-40 per 30-90 parts by weight of electrolyte solution.
39. The preparing method of lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to any one of claims 22 or 37 to 38, wherein solvents have the best ratio of ethylene carbonate (EC) per ethyl methyl carbonate (EMC) per dimethyl carbonate (DMC) of 25 per 5 per 70 parts by weight of electrolyte solution.
40. The preparing method of lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to either claim 22 or 37, wherein preferred additives comprise vinylene carbonate (VC) in the amount of 2 percent by weight of electrolyte solution, combined with any one of fluoroethylene carbonate (FEC), propane sultone (PS), lithium difluorophosphate (LiPO2F2), methylene methanedisulfonate (MMDS) additives or combination thereof in the amount of 0.1-10 percent by weight of electrolyte solution.
41. The preparing method of lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to any one of claim 22 or 37 or 40, wherein the most preferable additives comprise vinylene carbonate (VC) and fluoroethylene carbonate (FEC) in amounts of 2 and 0.1 percent by weight of electrolyte solution, respectively.
42. The preparing method of lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to either claim 22 or 37, wherein the most preferable electrolyte solution comprises lithium hexafluorophosphate at a concentration of 1.2 molars in ethylene carbonate (EC) per ethyl methyl carbonate (EMC) per dimethyl carbonate (DMC) solvents at 25 per 5 per 70 parts by weight, and vinylene carbonate (VC) and fluoroethylene carbonate (FEC) additives in amounts of 2 and 0. 1 percent by weight of electrolyte solution, respectively.
43. The preparing method of lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to claim 22, wherein the positive electrode prepared and coated on the aluminium foil has the positive electrode’s weight in a range of 17-23 milligrams per square centimetre and thickness in a range of 110-250 micrometres.
44. The preparing method of lithium-ion battery with positive electrode containing NMC material as the core and carbon black as the shell according to claim 22, wherein the negative electrode containing the negative electrode active material being graphite- type carbon or oxide material as prepared and coated on the copper foil has the negative electrode’s weight in a range of 10- 15 milligrams per square centimetre and thickness in a range of 100-250 micrometres.
PCT/TH2023/050009 2022-06-24 2023-06-17 Lithium-ion battery with positive electrode containing nmc material as the core and carbon black as the shell WO2023249567A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150349333A1 (en) * 2014-05-30 2015-12-03 Samsung Electronics Co., Ltd. Composite cathode active materials, preparation methods thereof, and lithium batteries including the composite cathode active materials
CA2994527A1 (en) * 2015-08-04 2017-02-09 Hitachi High-Technologies Corporation Non-aqueous electrolyte solution containing oxofluorophosphorous compounds
US20170062819A1 (en) * 2015-08-27 2017-03-02 Semiconductor Energy Laboratory Co., Ltd. Electrode, manufacturing method thereof, storage battery, and electronic device
US20170117589A1 (en) * 2015-10-27 2017-04-27 Semiconductor Energy Laboratory Co., Ltd. Power storage device electronic device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150349333A1 (en) * 2014-05-30 2015-12-03 Samsung Electronics Co., Ltd. Composite cathode active materials, preparation methods thereof, and lithium batteries including the composite cathode active materials
CA2994527A1 (en) * 2015-08-04 2017-02-09 Hitachi High-Technologies Corporation Non-aqueous electrolyte solution containing oxofluorophosphorous compounds
US20170062819A1 (en) * 2015-08-27 2017-03-02 Semiconductor Energy Laboratory Co., Ltd. Electrode, manufacturing method thereof, storage battery, and electronic device
US20170117589A1 (en) * 2015-10-27 2017-04-27 Semiconductor Energy Laboratory Co., Ltd. Power storage device electronic device

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