WO2023203559A1 - Carbon-based layered material and electrolyte compositions comprising the same - Google Patents
Carbon-based layered material and electrolyte compositions comprising the same Download PDFInfo
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- WO2023203559A1 WO2023203559A1 PCT/IL2023/050386 IL2023050386W WO2023203559A1 WO 2023203559 A1 WO2023203559 A1 WO 2023203559A1 IL 2023050386 W IL2023050386 W IL 2023050386W WO 2023203559 A1 WO2023203559 A1 WO 2023203559A1
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- Prior art keywords
- electrolyte
- carbonate
- electrolyte composition
- lithium
- carbon
- Prior art date
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 151
- 239000000203 mixture Substances 0.000 title claims abstract description 85
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000000463 material Substances 0.000 title claims abstract description 66
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 62
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 76
- 239000007788 liquid Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 33
- 230000001965 increasing effect Effects 0.000 claims abstract description 23
- 150000002500 ions Chemical class 0.000 claims abstract description 14
- 239000006185 dispersion Substances 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 35
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 31
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 31
- 238000004146 energy storage Methods 0.000 claims description 30
- 229910001416 lithium ion Inorganic materials 0.000 claims description 27
- 239000011877 solvent mixture Substances 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 19
- 239000011230 binding agent Substances 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 11
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 11
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims description 11
- 239000011149 active material Substances 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 10
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000006182 cathode active material Substances 0.000 claims description 9
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 5
- 229910052987 metal hydride Inorganic materials 0.000 claims description 5
- 150000004681 metal hydrides Chemical class 0.000 claims description 5
- 229910000652 nickel hydride Inorganic materials 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 229910052596 spinel Inorganic materials 0.000 claims description 5
- 239000011029 spinel Substances 0.000 claims description 5
- 229910012223 LiPFe Inorganic materials 0.000 claims description 4
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 4
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical compound [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-UHFFFAOYSA-N 0.000 claims description 4
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000003125 aqueous solvent Substances 0.000 claims description 4
- 230000000903 blocking effect Effects 0.000 claims description 4
- 239000003989 dielectric material Substances 0.000 claims description 4
- 239000000499 gel Substances 0.000 claims description 4
- 239000002608 ionic liquid Substances 0.000 claims description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 4
- CJYZTOPVWURGAI-UHFFFAOYSA-N lithium;manganese;manganese(3+);oxygen(2-) Chemical compound [Li+].[O-2].[O-2].[O-2].[O-2].[Mn].[Mn+3] CJYZTOPVWURGAI-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 230000021148 sequestering of metal ion Effects 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 2
- 229910001290 LiPF6 Inorganic materials 0.000 claims 1
- 239000006183 anode active material Substances 0.000 claims 1
- 229910052681 coesite Inorganic materials 0.000 claims 1
- 229910052906 cristobalite Inorganic materials 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 229910052682 stishovite Inorganic materials 0.000 claims 1
- 229910052905 tridymite Inorganic materials 0.000 claims 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 10
- 238000005259 measurement Methods 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 230000000149 penetrating effect Effects 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000002156 adsorbate Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000006194 liquid suspension Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- MSSUFHMGCXOVBZ-UHFFFAOYSA-N anthraquinone-2,6-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 MSSUFHMGCXOVBZ-UHFFFAOYSA-N 0.000 description 1
- 230000032770 biofilm formation Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/08—Selection of materials as electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/34—Gastight accumulators
- H01M10/345—Gastight metal hydride accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
Definitions
- the present invention relates in general to nanocarbon products. Particularly present invention relates to nanocarbon product blended into the electrolyte compositions and use thereof in manufacturing of the energy storage devices.
- Nanocarbon materials have recently been widely utilised in energy storage devices, because they are suitable for increasing the electric conductivity of commercial electrode materials at already very low mass percentage.
- Various geometries of carbon and graphitic carbon have been tested, such as a rod, plates, paper, felt, cloth, mesh, brush, and granules. Because the irregular physical structure of some of these materials, the electrical resistance is greater than desirable, others present a low specific surface area for biofilm formation, or high charge transfer resistance.
- Ideal characteristics of anode electrodes include high electrical conductivity, chemically inert, resistance to corrosion, mechanical resistance, high electrochemically active area, high specific surface area, biocompatible, and low-cost.
- Modifications of the surface of materials can be grouped as chemical and physical. Chemical modifications include coverage with conducting polymers, such as polyaniline, an increase of surface chemical groups, such as ammonium or quinones, and incorporation of electroactive compounds, such as FeiCh, RuCh, or AQDS, in the form of composites. Physical modifications are an increase of porosity by heating at high temperatures and an increase of roughness by incorporation of nanotubes.
- conducting polymers such as polyaniline
- surface chemical groups such as ammonium or quinones
- electroactive compounds such as FeiCh, RuCh, or AQDS
- nanocarbon materials have provided numerous application- specific efficient electrodes for energy storage and conversion, yet there are many more promises contained in the properties of nanocarbon materials which either have not been invented or need further refining or modification for commercial level applications.
- flexible and wearable energy devices are very attractive for portable electronic systems.
- Carbon-based lightweight structural energy storing systems are crucial for future communication vehicles on ground, through water, and in the air.
- load-bearing carbon structures for energy systems are desirable for advanced applications.
- Metal-air battery and solid-state electrolyte batteries are very promising to achieve higher energy and power density beyond their present state. No doubt, further innovation in nanocarbon materials fabrication, processing and applicability is essential for commercial level success in this field.
- the present invention relates to a method for preparing an electrolyte composition, said method comprises blending a nanocarbon material in an electrolyte, thereby creating a flowing liquid dispersion, wherein said nanocarbon material has a carbon particle size from about 0.5 microns to about 1000.0 microns and comprises a plurality of carbon layers, wherein each said carbon layer has a surface wetted with said electrolyte, wherein the thickness of each said carbon layer is from about 20 nm to about 120 nm, wherein the gap between the carbon layers is from about 0.5 gm (microns) to about 30 gm (microns), and wherein said nanocarbon material and the wetted surface of said carbon layers are suitable for increasing a battery electrode capacity and ions mobility.
- a contact angle of drops of the electrolyte to the wetted surface of the carbon layers is less than 90°, or from about 10° to about 40°, or from about 15° to about 30°.
- said nanocarbon material has a high metal-ion storage capacity of approximately 6.24 x 10 17 Li-ions per 1 mm 2 .
- the surface area of the carbon layers is in the range of about 100.0 m 2 /gr to about 400.0 m 2 /gr.
- the nanocarbon material is mixed with a graphite powder or with a cathode powder comprising a cathode active material.
- the cathode active materials are Lithium Nickel Cobalt Manganese Oxide (LiNiCoMnO2), Lithium Iron Phosphate (LiFePO4), Lithium Nickel Manganese Spinel (LiNio.5Mn1.5O4), Lithium Nickel Cobalt Aluminium Oxide (LiNiCoAlO2), Lithium Manganese Oxide (LiMn2O4) and Lithium Cobalt Oxide (LiCoO2).
- said nanocarbon material is blended inside said electrolyte composition, thereby creating a flowing liquid dispersion.
- the electrolyte can be either liquid or solid.
- the electrolyte composition comprises ionic liquid, polymer gel, solid, liquid or semi liquid to be solidified further on in the process.
- said electrolyte further comprising an electrolyte liquid or solvent.
- the electrolyte liquid or solvent are ethylene carbonate, ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, vinylene carbonate and aqueous solution of inorganic salts.
- the electrolyte composition further comprises a lithium hexafluorophosphate (LiPFe).
- LiPFe lithium hexafluorophosphate
- the nanocarbon material is blended inside said electrolyte composition in the concentration ratio of about 0.01-1.0% of the electrolyte by weight.
- Non-limiting examples of the electrolyte composition of the present invention are: a) 1.0- 1.4 M of lithium hexafluorophosphate in a solvent mixture of ethylene carbonate with ethyl methyl carbonate having the weight ratio 2.0-4.0:5.0-8.0 (wt/wt); b) 0.8-1.2 M of lithium hexafluorophosphate in a solvent mixture of ethylene carbonate with diethyl carbonate having the weight ratio 2.0-4.0:5.0-8.0 (wt/wt); c) 1.1 -1.5 M of lithium hexafluorophosphate in a solvent mixture of ethylene carbonate with dimethyl carbonate and ethyl methyl carbonate having the weight ratio 25-35:30-40:25-35 (wt/wt); d) 0.8-1.2 M of lithium hexafluorophosphate in a solvent mixture of ethylene carbonate with ethyl methyl carbonate having the weight ratio 40-60:40-60 (wt/wt); and e)
- the electrolyte composition is suitable for use in preparing a cathode electrolyte substrate for increasing a cathode capacity. In yet further embodiment, the electrolyte composition is suitable for use preparing an anode electrolyte substrate for increasing an anode capacity.
- an electrolyte composition comprises the nanocarbon material of the present invention, wherein said nanocarbon material is blended inside said electrolyte composition, thereby creating an aqueous flowing dispersion or liquid suspension.
- the electrolyte composition of the present invention comprises lithium hexafluorophosphate and a solvent or mixture of solvents selected from ethylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, and ethyl methyl carbonate.
- the electrolyte composition of the present invention comprises approximately 0.01-1.0% of said nanocarbon material by weight of the above electrolyte.
- an energy storage device comprises the electrolyte composition of the present invention and further comprises: a) A cathode prepared from a composition containing an active material and a binder and coated on a current collector; b) An anode prepared from a composition containing an active material and a binder and coated on a current collector; and c) Separator between the cathode and anode, said separator constitutes an electric insulator allowing ions movement via pores, but blocking an electron flow.
- the energy storage device of the present invention is selected from a supercapacitor of either an aqueous or organic solvent electrolyte type, nickel/metal hydride battery, lead-acid battery, Li-ion batteries and Li-ion polymer battery.
- the present invention relates to use of the electrolyte composition of the present invention in an anode electrolyte substrate for increased capacity of the anode of energy storage devices.
- the present invention relates to use of the electrolyte composition of the present invention in a cathode electrolyte substrate for increased capacity of the cathode of energy storage devices.
- Fig. la shows the scanning -electron microscope (SEM, Zeiss) image of the nanocarbon layered product of the present invention. Magnification is 25.00k X, scan speed is 1, system vacuum is 3.87 x 10’ 6 mbar, EHT is 3.0 kV, ESB grid is 0 V, aperture size is 30.00 pm, and focus is 5.2 mm.
- SEM scanning -electron microscope
- Fig. lb shows the scanning-electron microscope (SEM, Zeiss) image of the nanocarbon layered product of the present invention. The structure of the nanocarbon layered product and the distance between layers are clearly visible.
- Fig. 1c schematically shows the multi-layered nanocarbon structure of the product of the present invention.
- Fig. Id shows the bar chart for the distance distribution between the nanocarbon layers.
- Fig. 2 shows the BET multi-point results of the BET measurements of the nanocarbon layered product of the present invention.
- Weight of the sample is 0.1085 g
- adsorbate is nitrogen
- duration is 154.93 min.
- the obtained surface area is 296.764 m 2 /g.
- Fig. 3a shows the scanning electron microscope (SEM, Zeiss) image of Li ions moving into nanocarbon multi-layered material penetrating between carbon layers.
- SEM scanning electron microscope
- Fig. 3b schematically shows the Li ions movement between two adjacent nanocarbon layers of the product of the present invention.
- Fig. 4a schematically shows the wettability degree between a nanocarbon layer and an electrolyte drop.
- FIGs. 4b and 4c show the snapshots from OCA15EC optical contact angle measurements by DataPhysics Instruments GmbH (Germany).
- the terms “about” and “approximately” are understood as within a range of normal tolerance in the art, for example within two standard deviations of the mean.
- the term “about” means within 10% of the reported numerical value of the number with which it is being used, preferably within 5% of the reported numerical value.
- the term “about” can be immediately understood as within 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, 0.05%, or 0.01% of the stated value.
- the term “about” can mean a higher tolerance of variation depending on for instance the experimental technique used.
- an “electrolyte” is a medium, which contains ions, that is electrically conducting through the movement of those ions, but not conducting electrons. This includes most soluble salts, acids, and bases dissolved in a polar solvent, such as water. Upon dissolving, the substance separates into cations and anions, which disperse uniformly throughout the solvent. Electrically, such a solution is neutral. If an electric potential is applied to such a solution, the cations of the solution are drawn to the electrode that has an abundance of electrons, while the anions are drawn to the electrode that has a deficit of electrons. The movement of anions and cations in opposite directions within the solution creates a current.
- nanocarbon materials define nanomaterials composed of carbon atoms arranged in various geometries.
- Non-limiting examples of the nanocarbon materials are Ceo and other fullerenes arranged in the form of cages, carbon nanotubes (CNTs, single-walled or multiwalled) arranged in the form of tubes, and graphene arranged in the form of sheets.
- an electrolyte composition comprises the nanocarbon material.
- the nanocarbon material of the present invention is blended inside this composition and creates a flowing liquid dispersion.
- the electrolyte composition comprises approximately 0.01-1.0% of said nanocarbon material by weight of the aforementioned electrolyte.
- the present invention relates to a method for preparing an electrolyte composition, said method comprises blending a nanocarbon material in an electrolyte, thereby creating a flowing liquid dispersion, wherein said nanocarbon material having carbon particle size from about 0.5 microns (gm) to about 1000.0 microns (gm) and comprising a plurality of carbon layers, wherein each said carbon layer has a surface wetted with said electrolyte, wherein the thickness of said carbon layers is from about 20 nm to about 120 nm, wherein the gap between the carbon layers is from about 0.5 microns (pm) to about 30 microns (gm), wherein said nanocarbon material and the wetted surface of said carbon layers are designed to increase a battery electrode capacity and ions mobility.
- the term “wetted surface” means that the surface of the nanocarbon material or of each individual carbon layer is wetted with the electrolyte. The aspect of “wettability” will be discussed further in the description.
- said nanocarbon material has a high metal-ion storage capacity of approximately 6.24 x 10 17 Li-ions per 1 mm 2 .
- the surface area of the carbon layers is in the range of about 100.0 m 2 /gr to about 400.0 m 2 /gr.
- the nanocarbon material is mixed with a graphite powder or with a cathode powder comprising a cathode active material.
- the cathode active materials are Lithium Nickel Cobalt Manganese Oxide (LiNiCoMnO2), Lithium Iron Phosphate (LiFePO4), Lithium Nickel Manganese Spinel (LiNio.5Mn1.5O4), Lithium Nickel Cobalt Aluminium Oxide (LiNiCoAlO2), Lithium Manganese Oxide (LiMn2O4) and Lithium Cobalt Oxide (LiCoO2).
- said nanocarbon material is blended inside said electrolyte composition, thereby creating a flowing liquid dispersion.
- the electrolyte can be either liquid or solid.
- the electrolyte composition comprises ionic liquid, polymer gel, solid, liquid or semi liquid to be solidified further on in the process.
- said electrolyte further comprising an electrolyte liquid or solvent.
- Non-limiting examples of the electrolyte liquid or solvent are ethylene carbonate, ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, vinylene carbonate and aqueous solution of inorganic salts.
- the electrolyte composition further comprises a lithium hexafluorophosphate (LiPFe).
- the nanocarbon material is blended inside said electrolyte composition in the concentration ratio of about 0.01-1.0% of the electrolyte by weight.
- the electrolyte composition of the present invention are: a) 1.0- 1.4 M of lithium hexafluorophosphate in a solvent mixture of ethylene carbonate with ethyl methyl carbonate having the weight ratio 2.0-4.0:5.0-8.0 (wt/wt); b) 0.8-1.2 M of lithium hexafluorophosphate in a solvent mixture of ethylene carbonate with diethyl carbonate having the weight ratio 2.0-4.0:5.0-8.0 (wt/wt); c) 1.1 -1.5 M of lithium hexafluorophosphate in a solvent mixture of ethylene carbonate with dimethyl carbonate and ethyl methyl carbonate having the weight ratio 25-35:30-40:25-35 (wt/wt); d) 0.8-1.2 M of lithium hexafluorophosphat
- the electrolyte composition is suitable for use in preparing a cathode electrolyte substrate for increasing a cathode capacity. In yet further embodiment, the electrolyte composition is suitable for use preparing an anode electrolyte substrate for increasing an anode capacity.
- an electrolyte composition comprises the nanocarbon material of the present invention, wherein said nanocarbon material is blended inside said electrolyte composition, thereby creating a liquid flowing dispersion or liquid suspension.
- the electrolyte composition of the present invention comprises lithium hexafluorophosphate and a solvent or mixture of solvents selected from ethylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, and ethyl methyl carbonate.
- the electrolyte composition of the present invention comprises approximately 0.01-1.0% of said nanocarbon material by weight of the above electrolyte.
- an energy storage device comprises the electrolyte composition of the present invention and further comprises: a) A cathode prepared from a composition containing an active material and a binder and coated on a current collector; b) An anode prepared from a composition containing an active material and a binder and coated on a current collector; and c) Separator between the cathode and anode, said separator constitutes an electric insulator allowing ions movement via pores, but blocking an electron flow.
- the energy storage device of the present invention is selected from a supercapacitor of either an aqueous or organic solvent electrolyte type, nickel/metal hydride battery, lead-acid battery, Li-ion batteries and Li-ion polymer battery.
- the present invention relates to use of the electrolyte composition of the present invention in an anode electrolyte substrate for increased capacity of the anode of energy storage devices.
- the present invention relates to use of the electrolyte composition of the present invention in a cathode electrolyte substrate for increased capacity of the cathode of energy storage devices.
- SEM scanningelectron microscope
- Fig. la shows the scanning -electron microscope (SEM, Zeiss) image of the nanocarbon layered product of the present invention. Magnification is 25.00k X, scan speed is 1, system vacuum is 3.87 x 10’ 6 mbar, EHT is 3.0 kV, ESB grid is 0 V, aperture size is 30.00 pm, and focus is 5.2 mm.
- SEM scanning -electron microscope
- Fig. lb shows the scanning-electron microscope (SEM, Zeiss) image of the nanocarbon layered product of the present invention. The structure of the nanocarbon layered product and the distance between layers are clearly visible.
- Fig. 1c schematically shows the multi-layered nanocarbon structure of the product of the present invention.
- Fig. Id is the bar chart showing the distance distribution between the nanocarbon layers. Table 1 below summarises the distance distribution values from the bar chart for 50 measurements:
- the electrolyte penetrates into carbon nanomaterial wherein penetration being capillary mechanism of electrolyte moving between carbon layers.
- the reason for this mechanism is a very high wettability of the nanocarbon material as will be explained further in the description.
- the surface area of the layers of the nanocarbon material of the present invention is in the range of approximately 100.0 m 2 /gr to about 400.0 m 2 /gr.
- Fig. 2 showing the BET multi-point results of the BET measurements of the nanocarbon layered product of the present invention.
- Weight of the sample is 0.1085 g
- adsorbate is nitrogen
- duration is 154.93 min.
- the obtained BET of this product was found to be 296.764 m 2 /gr.
- graphite particles are added to the nanocarbon material comprising carbon layers.
- cathode active material particles are added to the nanocarbon material comprising carbon layers.
- the electrolyte composition of the present invention is used in preparing a cathode electrolyte substrate for increasing a cathode capacity. In another embodiment, the electrolyte composition of the present invention is used in preparing an anode electrolyte substrate for increasing an anode capacity.
- a non-limiting example of the electrolyte composition, in which the carbon-based layered material of the present invention is blended, is 1.2 M of the LFP6 in a solvent mixture of ethylene carbonate (EC) - ethyl methyl carbonate (EMC) having the weight ratio 3:7 (wt/wt), where LPF6 (lithium hexafluorophosphate, LiPFe) is an active component salt.
- EC ethylene carbonate
- EMC ethyl methyl carbonate
- the nanocarbon material of the present invention is blended in the electrolyte composition.
- the small gap between the layers of the nanocarbon material enhances ions absorption ability of the internal surface inside the layers, thereby generating the energy storage capacity.
- ions conductivity is created following the electrolyte penetrating between the carbon layers by a capillary mechanism.
- an energy storage device, or power cell, or battery comprises:
- a cathode prepared from a composition containing an active material and a binder and coated on aluminium, nickel or copper foil current collector.
- the coating thickness is normally in the range of 10 pm to 50 pm (micron).
- a suitable binder in the present invention are styrene butadiene copolymer (SBR), polyvinylidene fluoride (PVDF) and polyvinylidene difluoride (PVDDF) used in the cathode and anode electrode slurry making process for Li-ion batteries.
- Binders such as SBR, PVDF and PVDDF hold the active material particles together and in contact with the current collectors, i.e., the aluminium, nickel or copper foil.
- PVDF and PVDDF are highly non-reactive thermoplastic polymers produced by polymerisation of vinylidene difluoride and used in applications requiring the highest purity, as well as resistance to solvents, acids and hydrocarbons. Thanks to their high crystallinity levels, PVDF and PVDDF offer high resistance in typical electrolytes used in lithium batteries.
- the aforementioned binders may be mixed with Carbon Black to form a binder in the electrolyte composition of the present invention. In general, the binder is very important for mechanical stabilisation.
- Non-limiting examples of the cathode active materials are:
- NMC Lithium Nickel Cobalt Manganese Oxide
- LiFePO4 Lithium Iron Phosphate
- LiMn2O4 Lithium Manganese Oxide
- An anode prepared from a composition containing an active material and a binder coated, for example, on copper foil.
- a non-limiting example of the active material for the anode is a natural, synthetic or composite graphite.
- Graphite is a crystalline solid with a black/grey colour and a metallic sheen. Due to its electronic structure, it is highly conductive and can reach 25,000 S/cm 2 in the plane of a single crystal.
- Graphite is commonly used as the active material in negative electrodes mainly because it can reversibly place Li-ions between its many layers. This reversible electrochemical capability is maintained over several of thousands of cycles in batteries with optimised electrodes.
- the graphite surface must be compatible with the electrolyte solution and binders.
- suitable binders in this case are Carbon Black, SBR and carboxymethyl cellulose (CMC). These binders could increase the content of Li ions in the whole energy storage device (battery).
- the discharge platform of the battery is high and the degree of polarisation small, exhibiting excellent electrochemical performance.
- a polymer separator for example, polyethylene (PE) or polypropylene (PP), glass fibre (GF) having coating thickness of 10 pm to 50 pm (micron).
- PE polyethylene
- PP polypropylene
- GF glass fibre
- the terms “energy storage device”, “power cell” and “battery” are considered equivalent and used therefore interchangeably. These terms herein refer to batteries or super-capacitors comprised of at least one cell or a plurality of cells, such as Li-ion cells, connected in series, parallel or combinations thereof. Li-ions move from cathode to anode of the cell during the charge step, moving through the electrolyte. Ions move through separator pores of a nanometric size. Li-ions move from the anode to cathode during the discharge step.
- the polymer separator is an electric insulator, allowing ions movement via pores but blocking the electrons flow.
- the energy storage device is selected from a nickel/metal hydride batteries, lead-acid batteries, Li-ion batteries and Li-ion polymer batteries. In a specific embodiment, the energy storage device is a Li-ion cell.
- Fig. 3a showing the scanning electron microscope (SEM, Zeiss) image of Li ions moving into nanocarbon multi-layered material penetrating between carbon layers.
- SEM scanning electron microscope
- Magnification is 25.00k X
- scan speed is 1
- EHT is 3.0 kV
- ESB grid is 0 V
- focus is 5.2 mm
- aperture size is 30.00 pm
- system vacuum is 3.87 x 10’ 6 mbar.
- Fig. 3b schematically shows the Li ions movement between two adjacent nanocarbon layers of the product of the present invention.
- Fig. 4a schematically showing the wettability degree between a nanocarbon layer and electrolyte drop.
- Figs. 4b and 4c show the snapshots from OCA15EC optical contact angle measurements by DataPhysics Instruments GmbH (Germany).
- wetting or “wettability” is the ability of a liquid to maintain contact with a solid surface, and it is controlled by the balance between the intermolecular interactions of adhesive type (liquid to surface) and cohesive type (liquid to liquid). Wettability is characterised by a “contact angle”, which is the angle at which the liquid-vapor interface meets the solid-liquid interface. The contact angle is determined by the balance between the adhesive and cohesive forces.
- a wettable surface may also be termed hydrophilic and a non-wettable surface hydrophobic.
- Superhydrophobic surfaces have contact angles greater than 150°, showing almost no contact between the liquid drop and the surface.
- Hydrophilic surfaces as in the present invention have contact angles less than 90°, showing a very tight contact between the liquid drops and the surface.
- the nanocarbon layer is hydrophilic having the experimentally measured contact angle with the electrolyte drop approximately 30°.
- the electrolyte liquid in the present invention forms good contact with the nanocarbon layer and therefore, it spreads over the nanocarbon layers with strong adhesive interactions to these layers.
- Such high wettability of the electrolyte to the nanolayered carbon material is one of the aspects of the present invention.
- a contact angle of drops of the electrolyte to the wetted surface of the carbon layers is less than 90°, or from about 10° to about 40°, or from about 15° to about 30°.
- the electrolyte is added into the cell filling the space between the anode and separator, and between the cathode and separator.
- the electrolyte is then absorbed into both the cathode and anode coatings.
- the electrolyte penetrates into the carbon-based layered material of the present invention within the substrate of the power cell electrodes, thereby significantly enhancing mobility of the Li ions through the substrate and increasing conductivity of the power cell.
- the present inventors showed that the Li ions are efficiently adsorbed on the surface of the carbon-based layered material of the present invention inside the substrate.
- the present invention is used in non-energy storage devices using electrolyte.
- the carbon-based layered material of the present invention and the electrolyte composition comprising thereof are used in the anode electrolyte substrate for the increased capacity of the anode of the energy storage devices.
- Non-limiting examples of these devices are supercapacitors of either the aqueous or organic solvent electrolyte types, nickel/metal hydride batteries, lead-acid batteries, Li-ion cells and Li-ion polymer batteries.
- the nonlimiting examples of the anode powder comprises graphite, SiCL, Si or compositions of above for increased capacity of the cathode of the energy storage device.
- the carbon-based layered material of the present invention and the electrolyte composition comprising thereof are used in the cathode electrolyte substrate for the increased capacity of the cathode of the energy storage devices.
- the cathode-based materials comprise the mixture of the carbon-based layered material of the present invention and cathode powder.
- the non-limiting examples of the cathode powder comprises NCA, NMC811, NMC622, NMC532, LCO, LFP, LMO for increased capacity of the cathode of the energy storage device.
- the energy storage device comprises the cathode comprising graphite, the anode comprising lithium metal and the electrolyte composition comprising thereof of the present invention filling the power storage device.
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Abstract
An electrolyte composition and a method for preparing this electrolyte composition are described in the present invention. The method comprises blending a nanocarbon material in an electrolyte, thereby creating a flowing liquid dispersion, wherein said nanocarbon material has a carbon particle size from about 0.5 microns to about 1000.0 microns and comprises a plurality of carbon layers, wherein each said carbon layer has a surface wetted with said electrolyte, wherein the thickness of each said carbon layer is from about 20 nm to about 120 nm, wherein the gap between the carbon layers is from about 0.5 gm (microns) to about 30 gm (microns), and wherein said nanocarbon material and the wetted surface of said carbon layers are suitable for increasing a battery electrode capacity and ions mobility. A contact angle of drops of the electrolyte to the wetted surface of the carbon layers is less than 90°, or from about 10° to about 40°, or from about 15° to about 30°.
Description
CARBON-BASED LAYERED MATERIAL AND ELECTROLYTE COMPOSITIONS COMPRISING THE SAME
TECHNICAL FIELD
[0001] The present invention relates in general to nanocarbon products. Particularly present invention relates to nanocarbon product blended into the electrolyte compositions and use thereof in manufacturing of the energy storage devices.
BACKGROUND
[0002] Nanocarbon materials have recently been widely utilised in energy storage devices, because they are suitable for increasing the electric conductivity of commercial electrode materials at already very low mass percentage. Various geometries of carbon and graphitic carbon have been tested, such as a rod, plates, paper, felt, cloth, mesh, brush, and granules. Because the irregular physical structure of some of these materials, the electrical resistance is greater than desirable, others present a low specific surface area for biofilm formation, or high charge transfer resistance. To enhance the performance of nanocarbon materials several modifications have been proposed. Ideal characteristics of anode electrodes include high electrical conductivity, chemically inert, resistance to corrosion, mechanical resistance, high electrochemically active area, high specific surface area, biocompatible, and low-cost.
[0003] Modifications of the surface of materials can be grouped as chemical and physical. Chemical modifications include coverage with conducting polymers, such as polyaniline, an increase of surface chemical groups, such as ammonium or quinones, and incorporation of electroactive compounds, such as FeiCh, RuCh, or AQDS, in the form of composites. Physical modifications are an increase of porosity by heating at high temperatures and an increase of roughness by incorporation of nanotubes.
[0004] Although nanocarbon materials have provided numerous application- specific efficient electrodes for energy storage and conversion, yet there are many more promises contained in the properties of nanocarbon materials which either have not been invented or need further refining or modification for commercial level applications. Among such applications, flexible and wearable energy devices are very attractive for portable electronic systems. Carbon-based lightweight structural energy storing systems are crucial for future communication vehicles on ground, through water, and in the air. Furthermore, load-bearing carbon structures for energy systems are desirable for advanced
applications. Metal-air battery and solid-state electrolyte batteries are very promising to achieve higher energy and power density beyond their present state. No doubt, further innovation in nanocarbon materials fabrication, processing and applicability is essential for commercial level success in this field.
SUMMARY
[0005] The present invention relates to a method for preparing an electrolyte composition, said method comprises blending a nanocarbon material in an electrolyte, thereby creating a flowing liquid dispersion, wherein said nanocarbon material has a carbon particle size from about 0.5 microns to about 1000.0 microns and comprises a plurality of carbon layers, wherein each said carbon layer has a surface wetted with said electrolyte, wherein the thickness of each said carbon layer is from about 20 nm to about 120 nm, wherein the gap between the carbon layers is from about 0.5 gm (microns) to about 30 gm (microns), and wherein said nanocarbon material and the wetted surface of said carbon layers are suitable for increasing a battery electrode capacity and ions mobility.
[0006] In some embodiments, a contact angle of drops of the electrolyte to the wetted surface of the carbon layers is less than 90°, or from about 10° to about 40°, or from about 15° to about 30°.
[0007] In one embodiment, said nanocarbon material has a high metal-ion storage capacity of approximately 6.24 x 1017 Li-ions per 1 mm2. In some other embodiments, the surface area of the carbon layers is in the range of about 100.0 m2/gr to about 400.0 m2/gr.
[0008] In a certain embodiment, the nanocarbon material is mixed with a graphite powder or with a cathode powder comprising a cathode active material. Non-limiting examples of the cathode active materials are Lithium Nickel Cobalt Manganese Oxide (LiNiCoMnO2), Lithium Iron Phosphate (LiFePO4), Lithium Nickel Manganese Spinel (LiNio.5Mn1.5O4), Lithium Nickel Cobalt Aluminium Oxide (LiNiCoAlO2), Lithium Manganese Oxide (LiMn2O4) and Lithium Cobalt Oxide (LiCoO2).
[0009] In another embodiment, said nanocarbon material is blended inside said electrolyte composition, thereby creating a flowing liquid dispersion. The electrolyte can be either liquid or solid. [0010] In a particular embodiment, the electrolyte composition comprises ionic liquid, polymer gel, solid, liquid or semi liquid to be solidified further on in the process. In another particular embodiment, said electrolyte further comprising an electrolyte liquid or solvent. Non-limiting examples of the electrolyte liquid or solvent are ethylene carbonate, ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, vinylene carbonate and aqueous solution of inorganic salts. In a specific embodiment, the electrolyte composition further comprises a lithium hexafluorophosphate (LiPFe).
[0011] In still another embodiment, the nanocarbon material is blended inside said electrolyte composition in the concentration ratio of about 0.01-1.0% of the electrolyte by weight. Non-limiting examples of the electrolyte composition of the present invention are: a) 1.0- 1.4 M of lithium hexafluorophosphate in a solvent mixture of ethylene carbonate with ethyl methyl carbonate having the weight ratio 2.0-4.0:5.0-8.0 (wt/wt); b) 0.8-1.2 M of lithium hexafluorophosphate in a solvent mixture of ethylene carbonate with diethyl carbonate having the weight ratio 2.0-4.0:5.0-8.0 (wt/wt); c) 1.1 -1.5 M of lithium hexafluorophosphate in a solvent mixture of ethylene carbonate with dimethyl carbonate and ethyl methyl carbonate having the weight ratio 25-35:30-40:25-35 (wt/wt); d) 0.8-1.2 M of lithium hexafluorophosphate in a solvent mixture of ethylene carbonate with ethyl methyl carbonate having the weight ratio 40-60:40-60 (wt/wt); and e) 1.0- 1.4 M of lithium hexafluorophosphate in a solvent mixture of ethylene carbonate (EC) with ethyl methyl carbonate (EMC) having the weight ratio 2.0-4.0:5.0-8.0 (wt/wt) and vinylene carbonate (VC) 2% w/w.
[0012] In a further embodiment, the electrolyte composition is suitable for use in preparing a cathode electrolyte substrate for increasing a cathode capacity. In yet further embodiment, the electrolyte composition is suitable for use preparing an anode electrolyte substrate for increasing an anode capacity.
[0013] In another aspect of the present invention, an electrolyte composition comprises the nanocarbon material of the present invention, wherein said nanocarbon material is blended inside said electrolyte composition, thereby creating an aqueous flowing dispersion or liquid suspension. In some embodiments, the electrolyte composition of the present invention comprises lithium hexafluorophosphate and a solvent or mixture of solvents selected from ethylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, and ethyl methyl carbonate. In a particular embodiment, the electrolyte composition of the present invention comprises approximately 0.01-1.0% of said nanocarbon material by weight of the above electrolyte.
[0014] In a further aspect, an energy storage device comprises the electrolyte composition of the present invention and further comprises: a) A cathode prepared from a composition containing an active material and a binder and coated on a current collector;
b) An anode prepared from a composition containing an active material and a binder and coated on a current collector; and c) Separator between the cathode and anode, said separator constitutes an electric insulator allowing ions movement via pores, but blocking an electron flow.
[0015] In a specific embodiment, the energy storage device of the present invention is selected from a supercapacitor of either an aqueous or organic solvent electrolyte type, nickel/metal hydride battery, lead-acid battery, Li-ion batteries and Li-ion polymer battery.
[0016] In yet further aspect, the present invention relates to use of the electrolyte composition of the present invention in an anode electrolyte substrate for increased capacity of the anode of energy storage devices. In still another aspect, the present invention relates to use of the electrolyte composition of the present invention in a cathode electrolyte substrate for increased capacity of the cathode of energy storage devices.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] Disclosed embodiments will be understood and appreciated more fully from the following detailed description taken in conjunction with the appended figures. The drawings included and described herein are schematic and are not limiting the scope of the disclosure. It is also noted that in the drawings, the size of some elements may be exaggerated and, therefore, not drawn to scale for illustrative purposes. The dimensions and the relative dimensions do not necessarily correspond to actual reductions to practice of the disclosure.
[0018] Fig. la shows the scanning -electron microscope (SEM, Zeiss) image of the nanocarbon layered product of the present invention. Magnification is 25.00k X, scan speed is 1, system vacuum is 3.87 x 10’6 mbar, EHT is 3.0 kV, ESB grid is 0 V, aperture size is 30.00 pm, and focus is 5.2 mm.
[0019] Fig. lb shows the scanning-electron microscope (SEM, Zeiss) image of the nanocarbon layered product of the present invention. The structure of the nanocarbon layered product and the distance between layers are clearly visible.
[0020] Fig. 1c schematically shows the multi-layered nanocarbon structure of the product of the present invention. Fig. Id shows the bar chart for the distance distribution between the nanocarbon layers.
[0021] Fig. 2 shows the BET multi-point results of the BET measurements of the nanocarbon layered product of the present invention. Weight of the sample is 0.1085 g, adsorbate is nitrogen, duration is 154.93 min. The linear plot of the isotherm branch adsorption has the following parameters:
slope = 11.6392, intercept = 0.095484, correlation coefficient R = 0.999686, constant C = 122.561. The obtained surface area is 296.764 m2/g.
[0022] Fig. 3a shows the scanning electron microscope (SEM, Zeiss) image of Li ions moving into nanocarbon multi-layered material penetrating between carbon layers. Magnification is 25.00k X, scan speed is 1, system vacuum is 3.87 x 10’6 mbar, EHT is 3.0 kV, ESB grid is 0 V, focus is 5.2 mm, and aperture size is 30.00 pm.
[0023] Fig. 3b schematically shows the Li ions movement between two adjacent nanocarbon layers of the product of the present invention.
[0024] Fig. 4a schematically shows the wettability degree between a nanocarbon layer and an electrolyte drop.
[0025] Figs. 4b and 4c show the snapshots from OCA15EC optical contact angle measurements by DataPhysics Instruments GmbH (Germany).
DETAILED DESCRIPTION
[0026] In the following description, various aspects of the present invention will be described. For purposes of explanation, specific details are set forth in order to provide a thorough understanding of the present invention. However, it will also be apparent to one skilled in the art that the present invention may be practiced without the specific details presented herein. Furthermore, well-known features may be omitted or simplified in order not to obscure the present invention.
[0027] The term "comprising", used in the claims, is "open ended" and means the elements recited, or their equivalent in structure or function, plus any other element or elements which are not recited. It should not be interpreted as being restricted to the means listed thereafter; it does not exclude other elements or steps. It needs to be interpreted as specifying the presence of the stated features, integers, steps or components as referred to, but does not preclude the presence or addition of one or more other features, integers, steps or components, or groups thereof. Thus, the scope of the expression "a composition comprising x and z" should not be limited to compositions consisting only of components x and z. Also, the scope of the expression "a method comprising the steps x and z" should not be limited to methods consisting only of these steps.
[0028] Unless specifically stated, as used herein, the terms "about" and “approximately” are understood as within a range of normal tolerance in the art, for example within two standard deviations of the mean. In one embodiment, the term "about" means within 10% of the reported numerical value of the number with which it is being used, preferably within 5% of the reported numerical value. For
example, the term "about" can be immediately understood as within 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, 0.05%, or 0.01% of the stated value. In other embodiments, the term "about" can mean a higher tolerance of variation depending on for instance the experimental technique used. Said variations of a specified value are understood by the skilled person and are within the context of the present invention. As an illustration, a numerical range of "about 1 to about 5" should be interpreted to include not only the explicitly recited values of about 1 to about 5, but also include individual values and sub-ranges within the indicated range. Thus, included in this numerical range are individual values such as 2, 3, and 4 and sub-ranges, for example from 1-3, from 2-4, and from 3- 5, as well as 1, 2, 3, 4, 5, or 6, individually. This same principle applies to ranges reciting only one numerical value as a minimum or a maximum. Unless otherwise clear from context, all numerical values provided herein are modified by the term "about". Other similar terms, such as "substantially", "generally", "up to" and the like are to be construed as modifying a term or value such that it is not an absolute. Such terms will be defined by the circumstances and the terms that they modify as those terms are understood by those of skilled in the art. This includes, at very least, the degree of expected experimental error, technical error and instrumental error for a given experiment, technique or an instrument used to measure a value.
[0029] As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items. Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the specification and relevant art and should not be interpreted in an idealized or overly formal sense unless expressly so defined herein. Well-known functions or constructions may not be described in detail for brevity and/or clarity.
[0030] By definition, an “electrolyte” is a medium, which contains ions, that is electrically conducting through the movement of those ions, but not conducting electrons. This includes most soluble salts, acids, and bases dissolved in a polar solvent, such as water. Upon dissolving, the substance separates into cations and anions, which disperse uniformly throughout the solvent. Electrically, such a solution is neutral. If an electric potential is applied to such a solution, the cations of the solution are drawn to the electrode that has an abundance of electrons, while the anions are drawn to the electrode that has a deficit of electrons. The movement of anions and cations in opposite directions within the solution creates a current.
[0031] In the present invention, the term “nanocarbon materials” define nanomaterials composed of carbon atoms arranged in various geometries. Non-limiting examples of the nanocarbon materials are Ceo and other fullerenes arranged in the form of cages, carbon nanotubes (CNTs, single-walled or multiwalled) arranged in the form of tubes, and graphene arranged in the form of sheets. In the present invention, an electrolyte composition comprises the nanocarbon material. The nanocarbon material of the present invention is blended inside this composition and creates a flowing liquid dispersion. In a particular embodiment, the electrolyte composition comprises approximately 0.01-1.0% of said nanocarbon material by weight of the aforementioned electrolyte.
[0032] The present invention relates to a method for preparing an electrolyte composition, said method comprises blending a nanocarbon material in an electrolyte, thereby creating a flowing liquid dispersion, wherein said nanocarbon material having carbon particle size from about 0.5 microns (gm) to about 1000.0 microns (gm) and comprising a plurality of carbon layers, wherein each said carbon layer has a surface wetted with said electrolyte, wherein the thickness of said carbon layers is from about 20 nm to about 120 nm, wherein the gap between the carbon layers is from about 0.5 microns (pm) to about 30 microns (gm), wherein said nanocarbon material and the wetted surface of said carbon layers are designed to increase a battery electrode capacity and ions mobility. In the present invention, the term “wetted surface” means that the surface of the nanocarbon material or of each individual carbon layer is wetted with the electrolyte. The aspect of “wettability” will be discussed further in the description.
[0033] The reason for the certain range of the particle size of the nanocarbon material from 0.5 micron to 1000.0 microns, is that when the particles are larger than 1000 micron, the particles are not able to form a stable liquid dispersion in the electrolyte. When the particle size is smaller than 0.5 micron, the particles tend to increase the liquid dispersion viscosity, thereby negatively affecting the liquid electrolyte dispersion flow ability.
[0034] In one embodiment, said nanocarbon material has a high metal-ion storage capacity of approximately 6.24 x 1017 Li-ions per 1 mm2. In some other embodiments, the surface area of the carbon layers is in the range of about 100.0 m2/gr to about 400.0 m2/gr.
[0035] In a certain embodiment, the nanocarbon material is mixed with a graphite powder or with a cathode powder comprising a cathode active material. Non-limiting examples of the cathode active materials are Lithium Nickel Cobalt Manganese Oxide (LiNiCoMnO2), Lithium Iron Phosphate (LiFePO4), Lithium Nickel Manganese Spinel (LiNio.5Mn1.5O4), Lithium Nickel Cobalt Aluminium Oxide (LiNiCoAlO2), Lithium Manganese Oxide (LiMn2O4) and Lithium Cobalt Oxide (LiCoO2).
[0036] In another embodiment, said nanocarbon material is blended inside said electrolyte composition, thereby creating a flowing liquid dispersion. The electrolyte can be either liquid or solid. [0037] In a particular embodiment, the electrolyte composition comprises ionic liquid, polymer gel, solid, liquid or semi liquid to be solidified further on in the process. In another particular embodiment, said electrolyte further comprising an electrolyte liquid or solvent. Non-limiting examples of the electrolyte liquid or solvent are ethylene carbonate, ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, vinylene carbonate and aqueous solution of inorganic salts. In a specific embodiment, the electrolyte composition further comprises a lithium hexafluorophosphate (LiPFe).
[0038] In still another embodiment, the nanocarbon material is blended inside said electrolyte composition in the concentration ratio of about 0.01-1.0% of the electrolyte by weight. Non-limiting examples of the electrolyte composition of the present invention are: a) 1.0- 1.4 M of lithium hexafluorophosphate in a solvent mixture of ethylene carbonate with ethyl methyl carbonate having the weight ratio 2.0-4.0:5.0-8.0 (wt/wt); b) 0.8-1.2 M of lithium hexafluorophosphate in a solvent mixture of ethylene carbonate with diethyl carbonate having the weight ratio 2.0-4.0:5.0-8.0 (wt/wt); c) 1.1 -1.5 M of lithium hexafluorophosphate in a solvent mixture of ethylene carbonate with dimethyl carbonate and ethyl methyl carbonate having the weight ratio 25-35:30-40:25-35 (wt/wt); d) 0.8-1.2 M of lithium hexafluorophosphate in a solvent mixture of ethylene carbonate with ethyl methyl carbonate having the weight ratio 40-60:40-60 (wt/wt); and e) 1.0- 1.4 M of lithium hexafluorophosphate in a solvent mixture of ethylene carbonate (EC) with ethyl methyl carbonate (EMC) having the weight ratio 2.0-4.0:5.0-8.0 (wt/wt) and vinylene carbonate (VC) 2% w/w.
[0039] In a further embodiment, the electrolyte composition is suitable for use in preparing a cathode electrolyte substrate for increasing a cathode capacity. In yet further embodiment, the electrolyte composition is suitable for use preparing an anode electrolyte substrate for increasing an anode capacity.
[0040] In another aspect of the present invention, an electrolyte composition comprises the nanocarbon material of the present invention, wherein said nanocarbon material is blended inside said electrolyte composition, thereby creating a liquid flowing dispersion or liquid suspension. In some embodiments, the electrolyte composition of the present invention comprises lithium hexafluorophosphate and a solvent or mixture of solvents selected from ethylene carbonate, ethyl
methyl carbonate, diethyl carbonate, dimethyl carbonate, and ethyl methyl carbonate. In a particular embodiment, the electrolyte composition of the present invention comprises approximately 0.01-1.0% of said nanocarbon material by weight of the above electrolyte.
[0041] In a further aspect, an energy storage device comprises the electrolyte composition of the present invention and further comprises: a) A cathode prepared from a composition containing an active material and a binder and coated on a current collector; b) An anode prepared from a composition containing an active material and a binder and coated on a current collector; and c) Separator between the cathode and anode, said separator constitutes an electric insulator allowing ions movement via pores, but blocking an electron flow.
[0042] In a specific embodiment, the energy storage device of the present invention is selected from a supercapacitor of either an aqueous or organic solvent electrolyte type, nickel/metal hydride battery, lead-acid battery, Li-ion batteries and Li-ion polymer battery.
[0043] In yet further aspect, the present invention relates to use of the electrolyte composition of the present invention in an anode electrolyte substrate for increased capacity of the anode of energy storage devices. In still another aspect, the present invention relates to use of the electrolyte composition of the present invention in a cathode electrolyte substrate for increased capacity of the cathode of energy storage devices. Reference is now made to Figs, la and lb showing the scanningelectron microscope (SEM) images of the carbon-based layered product of the present invention.
[0044] Fig. la shows the scanning -electron microscope (SEM, Zeiss) image of the nanocarbon layered product of the present invention. Magnification is 25.00k X, scan speed is 1, system vacuum is 3.87 x 10’6 mbar, EHT is 3.0 kV, ESB grid is 0 V, aperture size is 30.00 pm, and focus is 5.2 mm.
[0045] Fig. lb shows the scanning-electron microscope (SEM, Zeiss) image of the nanocarbon layered product of the present invention. The structure of the nanocarbon layered product and the distance between layers are clearly visible. Fig. 1c schematically shows the multi-layered nanocarbon structure of the product of the present invention. Fig. Id is the bar chart showing the distance distribution between the nanocarbon layers. Table 1 below summarises the distance distribution values from the bar chart for 50 measurements:
Table 1. Distance distribution values from the bar chart for 50 measurements.
[0046] In the present invention, the electrolyte penetrates into carbon nanomaterial wherein penetration being capillary mechanism of electrolyte moving between carbon layers. The reason for this mechanism is a very high wettability of the nanocarbon material as will be explained further in the description.
[0047] In some embodiments, the surface area of the layers of the nanocarbon material of the present invention is in the range of approximately 100.0 m2/gr to about 400.0 m2/gr. Reference is now made to Fig. 2 showing the BET multi-point results of the BET measurements of the nanocarbon layered product of the present invention. Weight of the sample is 0.1085 g, adsorbate is nitrogen, duration is 154.93 min. The linear plot of the isotherm branch adsorption has the following parameters: slope = 11.6392, intercept = 0.095484, correlation coefficient R = 0.999686, constant C = 122.561. The obtained BET of this product was found to be 296.764 m2/gr.
[0048] In a further embodiment, graphite particles are added to the nanocarbon material comprising carbon layers. In yet further embodiment, cathode active material particles are added to the nanocarbon material comprising carbon layers.
[0049] In one embodiment, the electrolyte composition of the present invention is used in preparing a cathode electrolyte substrate for increasing a cathode capacity. In another embodiment, the electrolyte composition of the present invention is used in preparing an anode electrolyte substrate for increasing an anode capacity.
[0050] A non-limiting example of the electrolyte composition, in which the carbon-based layered material of the present invention is blended, is 1.2 M of the LFP6 in a solvent mixture of ethylene carbonate (EC) - ethyl methyl carbonate (EMC) having the weight ratio 3:7 (wt/wt), where LPF6 (lithium hexafluorophosphate, LiPFe) is an active component salt.
[0051] In yet further embodiment, the nanocarbon material of the present invention is blended in the electrolyte composition. As mentioned above, the small gap between the layers of the nanocarbon
material enhances ions absorption ability of the internal surface inside the layers, thereby generating the energy storage capacity. Thus, ions conductivity is created following the electrolyte penetrating between the carbon layers by a capillary mechanism.
[0052] In another embodiment, an energy storage device, or power cell, or battery comprises:
1) A cathode prepared from a composition containing an active material and a binder and coated on aluminium, nickel or copper foil current collector. The coating thickness is normally in the range of 10 pm to 50 pm (micron). Non-limiting examples of a suitable binder in the present invention are styrene butadiene copolymer (SBR), polyvinylidene fluoride (PVDF) and polyvinylidene difluoride (PVDDF) used in the cathode and anode electrode slurry making process for Li-ion batteries. Binders such as SBR, PVDF and PVDDF hold the active material particles together and in contact with the current collectors, i.e., the aluminium, nickel or copper foil. PVDF and PVDDF are highly non-reactive thermoplastic polymers produced by polymerisation of vinylidene difluoride and used in applications requiring the highest purity, as well as resistance to solvents, acids and hydrocarbons. Thanks to their high crystallinity levels, PVDF and PVDDF offer high resistance in typical electrolytes used in lithium batteries. The aforementioned binders may be mixed with Carbon Black to form a binder in the electrolyte composition of the present invention. In general, the binder is very important for mechanical stabilisation. Non-limiting examples of the cathode active materials are:
■ NMC (NCM) - Lithium Nickel Cobalt Manganese Oxide (LiNiCoMnO2)
■ LFP - Lithium Iron Phosphate (LiFePO4)
■ LNMO - Lithium Nickel Manganese Spinel (LiNio.5Mn1.5O4)
■ NCA - Lithium Nickel Cobalt Aluminium Oxide (LiNiCoAlO2)
■ LMO - Lithium Manganese Oxide (LiMn2O4)
■ LCO - Lithium Cobalt Oxide (LiCoO2).
2) An anode prepared from a composition containing an active material and a binder coated, for example, on copper foil. A non-limiting example of the active material for the anode is a natural, synthetic or composite graphite. Graphite is a crystalline solid with a black/grey colour and a metallic sheen. Due to its electronic structure, it is highly conductive and can reach 25,000 S/cm2 in the plane of a single crystal. Graphite is commonly used as the active material in negative electrodes mainly because it can reversibly place Li-ions between its many layers. This reversible electrochemical capability is maintained over several of thousands of cycles in batteries with optimised electrodes. However, one requirement for this application is that the graphite surface
must be compatible with the electrolyte solution and binders. Non-limiting examples of the suitable binders in this case are Carbon Black, SBR and carboxymethyl cellulose (CMC). These binders could increase the content of Li ions in the whole energy storage device (battery). The discharge platform of the battery is high and the degree of polarisation small, exhibiting excellent electrochemical performance.
3) A polymer separator, for example, polyethylene (PE) or polypropylene (PP), glass fibre (GF) having coating thickness of 10 pm to 50 pm (micron).
[0053] In the present invention, the terms “energy storage device”, “power cell” and “battery” are considered equivalent and used therefore interchangeably. These terms herein refer to batteries or super-capacitors comprised of at least one cell or a plurality of cells, such as Li-ion cells, connected in series, parallel or combinations thereof. Li-ions move from cathode to anode of the cell during the charge step, moving through the electrolyte. Ions move through separator pores of a nanometric size. Li-ions move from the anode to cathode during the discharge step. The polymer separator is an electric insulator, allowing ions movement via pores but blocking the electrons flow.
[0054] In a particular embodiment, the energy storage device is selected from a nickel/metal hydride batteries, lead-acid batteries, Li-ion batteries and Li-ion polymer batteries. In a specific embodiment, the energy storage device is a Li-ion cell.
[0055] Reference is now made to Fig. 3a showing the scanning electron microscope (SEM, Zeiss) image of Li ions moving into nanocarbon multi-layered material penetrating between carbon layers. Magnification is 25.00k X, scan speed is 1, EHT is 3.0 kV, ESB grid is 0 V, focus is 5.2 mm, aperture size is 30.00 pm, and system vacuum is 3.87 x 10’6 mbar. Fig. 3b schematically shows the Li ions movement between two adjacent nanocarbon layers of the product of the present invention.
[0056] Reference is now made to Fig. 4a schematically showing the wettability degree between a nanocarbon layer and electrolyte drop. Figs. 4b and 4c show the snapshots from OCA15EC optical contact angle measurements by DataPhysics Instruments GmbH (Germany). By definition, “wetting” or “wettability” is the ability of a liquid to maintain contact with a solid surface, and it is controlled by the balance between the intermolecular interactions of adhesive type (liquid to surface) and cohesive type (liquid to liquid). Wettability is characterised by a “contact angle”, which is the angle at which the liquid-vapor interface meets the solid-liquid interface. The contact angle is determined by the balance between the adhesive and cohesive forces. As the tendency of a drop to spread out over a flat, solid surface increases, the contact angle decreases. Thus, the contact angle provides an inverse
measure of wettability. Table 2 below summarises the contact angle measurements of the electrolyte drops to the nanolayered carbon material surface of the present invention.
Table 2. Contact angle measurements of the electrolyte drops to the nanolayered carbon material surface.
Abbreviations and units used in the table: CA - contact angle [°] ; (M) - mean value; (R) - right side; (L) - left side; IFT - interfacial tension [mN/m]; Err - fitting error [pm]; Vol - drop volume [pl].
[0057] Contact angles less than 90° (low contact angle) generally mean that wettability of the surface is favourable, so the fluid will maximise contact with the wetted surface and spread over the entire surface. For water, a wettable surface may also be termed hydrophilic and a non-wettable surface hydrophobic. Superhydrophobic surfaces have contact angles greater than 150°, showing almost no contact between the liquid drop and the surface. Hydrophilic surfaces as in the present invention, have contact angles less than 90°, showing a very tight contact between the liquid drops and the surface. As seen in Figs. 4a-4c, the nanocarbon layer is hydrophilic having the experimentally measured contact angle with the electrolyte drop approximately 30°. In other words, the electrolyte liquid in the present invention forms good contact with the nanocarbon layer and therefore, it spreads over the nanocarbon layers with strong adhesive interactions to these layers. Such high wettability of the electrolyte to the nanolayered carbon material is one of the aspects of the present invention. In some embodiments, a contact angle of drops of the electrolyte to the wetted surface of the carbon layers is less than 90°, or from about 10° to about 40°, or from about 15° to about 30°.
[0058] The electrolyte is added into the cell filling the space between the anode and separator, and between the cathode and separator. The electrolyte is then absorbed into both the cathode and anode coatings. Thus, the electrolyte penetrates into the carbon-based layered material of the present
invention within the substrate of the power cell electrodes, thereby significantly enhancing mobility of the Li ions through the substrate and increasing conductivity of the power cell. The present inventors showed that the Li ions are efficiently adsorbed on the surface of the carbon-based layered material of the present invention inside the substrate.
[0059] In yet another embodiment, the present invention is used in non-energy storage devices using electrolyte.
[0060] In a certain embodiment, the carbon-based layered material of the present invention and the electrolyte composition comprising thereof are used in the anode electrolyte substrate for the increased capacity of the anode of the energy storage devices. Non-limiting examples of these devices are supercapacitors of either the aqueous or organic solvent electrolyte types, nickel/metal hydride batteries, lead-acid batteries, Li-ion cells and Li-ion polymer batteries. As mentioned above, the nonlimiting examples of the anode powder comprises graphite, SiCL, Si or compositions of above for increased capacity of the cathode of the energy storage device.
[0061] In a certain embodiment, the carbon-based layered material of the present invention and the electrolyte composition comprising thereof are used in the cathode electrolyte substrate for the increased capacity of the cathode of the energy storage devices. In a particular embodiment, the cathode-based materials comprise the mixture of the carbon-based layered material of the present invention and cathode powder. As mentioned above, the non-limiting examples of the cathode powder comprises NCA, NMC811, NMC622, NMC532, LCO, LFP, LMO for increased capacity of the cathode of the energy storage device.
[0062] In a specific embodiment, the energy storage device comprises the cathode comprising graphite, the anode comprising lithium metal and the electrolyte composition comprising thereof of the present invention filling the power storage device.
Claims
1. A method for preparing an electrolyte composition, said method comprises blending a nanocarbon material in an electrolyte, thereby creating a flowing liquid dispersion, wherein said nanocarbon material has a carbon particle size from about 0.5 microns to about 1000.0 microns and comprises a plurality of carbon layers, wherein each said carbon layer has a surface wetted with said electrolyte, wherein the thickness of each said carbon layer is from about 20 nm to about 120 nm, wherein the gap between the carbon layers is from about 0.5 gm (microns) to about 30 pm (microns), and wherein said nanocarbon material and the wetted surface of said carbon layers are suitable for increasing a battery electrode capacity and ions mobility.
2. The method of claim 1 , wherein a contact angle of drops of said electrolyte to the wetted surface of said carbon layers is less than 90°.
3. The method of claim 2, wherein the contact angle of drops of said electrolyte to the wetted surface of said carbon layers is from about 10° to about 40°.
4. The method of claim 3, wherein the contact angle of drops of said electrolyte to the wetted surface of said carbon layers is from about 15° to about 30°.
5. The method of any one of claims 1 to 4, wherein said nanocarbon material has a metal-ion storage capacity of approximately 6.24 x 1017 Li-ions per 1 mm2.
6. The method of any one of claims 1 to 5, wherein each carbon layer in said nanocarbon material has a thickness in the range of about 20 nm to about 120 nm and the distance (gap) between the layers in the range of about 0.5 microns (gm) to about 30.0 microns (gm).
7. The method of any one of claims 1 to 6, wherein the surface area of the carbon layers is in the range of about 100.0 m2/gr to about 400.0 m2/gr.
8. The method of any one of claims 1 to 7, wherein said nanocarbon material is mixed with a graphite powder.
9. The method of any one of claims 1 to 8, wherein said nanocarbon material is mixed with a cathode powder comprising a cathode active material.
The method of claim 9, wherein cathode active material is selected from the group consisting of Lithium Nickel Cobalt Manganese Oxide (LiNiCoMnO2), Lithium Iron Phosphate (LiFePO4), Lithium Nickel Manganese Spinel (LiNio.5Mn1.5O4), Lithium Nickel Cobalt Aluminium Oxide (LiNiCoAlO2), Lithium Manganese Oxide (LiMn2O4) and Lithium Cobalt Oxide (LiCoO2). The method of any one of claims 1 to 10, wherein the electrolyte in said electrolyte composition comprises ionic liquid, polymer gel, solid, liquid or semi liquid to be solidified further on in the process. The method of any one of claims 1 to 11, wherein said electrolyte comprises an electrolyte liquid or solvent. The method of claim 12, wherein said electrolyte liquid or solvent is selected from the group consisting of ethylene carbonate, ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, vinylene carbonate and aqueous solution of inorganic salts. The method of any one of claims 1 to 13, further comprising a lithium hexafluorophosphate (LiPF6). The method of any one of claims 1 to 14, wherein said nanocarbon material is blended inside said electrolyte composition in the concentration ratio of about 0.01-1.0% of the electrolyte by weight. The method of any one of claims 1 to 15, wherein said electrolyte composition is selected from: a) 1.0- 1.4 M of lithium hexafluorophosphate in a solvent mixture of ethylene carbonate (EC) with ethyl methyl carbonate (EMC) having the weight ratio 2.0-4.0:5.0-8.0 (wt/wt); b) 0.8-1.2 M of lithium hexafluorophosphate in a solvent mixture of ethylene carbonate (EC) with diethyl carbonate (DEC) having the weight ratio 2.0-4.0:5.0-8.0 (wt/wt); c) 1.1 -1.5 M of lithium hexafluorophosphate in a solvent mixture of ethylene carbonate (EC) with dimethyl carbonate (DMC) and ethyl methyl carbonate (EMC) having the weight ratio 25-35:30-40:25-35 (wt/wt); d) 0.8-1.2 M of lithium hexafluorophosphate in a solvent mixture of ethylene carbonate (EC) with ethyl methyl carbonate (EMC) having the weight ratio 40-60:40-60 (wt/wt); and
e) 1.0- 1.4 M of lithium hexafluorophosphate in a solvent mixture of ethylene carbonate (EC) with ethyl methyl carbonate (EMC) having the weight ratio 2.0-4.0:5.0-8.0 (wt/wt) and vinylene carbonate (VC) 2% w/w. The method of any one of claims 1 to 16, wherein said electrolyte composition is suitable for use in preparing a cathode electrolyte substrate for increasing a cathode capacity or an anode capacity. The method of any one of claims 1 to 16, wherein said electrolyte composition is suitable for use preparing an anode electrolyte substrate for increasing an anode capacity. An electrolyte composition comprising a nanocarbon material having carbon particle size from about 0.5 microns (gm) to about 1000.0 microns (gm) and comprising a plurality of carbon layers, wherein each said carbon layer has a surface wetted with said electrolyte, wherein the thickness of said carbon layers is from about 20 nm to about 120 nm, wherein the gap between the carbon layers is from about 0.5 microns (gm) to about 30 microns (gm), wherein said nanocarbon material and the wetted surface of said carbon layers are designed to increase a battery electrode capacity and ions mobility, wherein said nanocarbon material is blended inside said electrolyte composition, thereby creating a flowing liquid dispersion. The electrolyte composition of claim 19, wherein a contact angle of drops of said electrolyte to the wetted surface of said carbon layers is less than 90°. The electrolyte composition of claim 20, wherein a contact angle of drops of said electrolyte to the wetted surface of said carbon layers is from about 10° to about 40°. The electrolyte composition of claim 21, wherein a contact angle of drops of said electrolyte to the wetted surface of said carbon layers is from about 15° to about 30°. The electrolyte composition of any one of claims 19 to 22, wherein said electrolyte can be either liquid or solid. The electrolyte composition of any one of claims 19 to 23, wherein the electrolyte in said electrolyte composition comprising ionic liquid, polymer gel, solid, liquid or semi liquid to be solidified further on in the process.
The electrolyte composition of any one of claims 19 to 24, wherein said electrolyte comprises an electrolyte liquid or solvent. The electrolyte composition of claim 25, wherein said electrolyte liquid or solvent is selected from the group consisting of ethylene carbonate, ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, vinylene carbonate and aqueous solution of inorganic salts. The electrolyte composition of any one of claims 19 to 26, further comprising a lithium hexafluorophosphate (LiPFe). The electrolyte composition of any one of claims 19 to 27, wherein said nanocarbon material is blended inside said electrolyte composition in the concentration ratio of about 0.01-1.0% of the electrolyte by weight. The electrolyte composition of any one of claims 19 to 28, wherein said electrolyte composition is selected from: a) 1.0- 1.4 M of lithium hexafluorophosphate in a solvent mixture of ethylene carbonate with ethyl methyl carbonate having the weight ratio 2.0-4.0:5.0-8.0 (wt/wt); b) 0.8-1.2 M of lithium hexafluorophosphate in a solvent mixture of ethylene carbonate with diethyl carbonate having the weight ratio 2.0-4.0:5.0-8.0 (wt/wt); c) 1.1 -1.5 M of lithium hexafluorophosphate in a solvent mixture of ethylene carbonate with dimethyl carbonate and ethyl methyl carbonate having the weight ratio 25-35:30-40:25-35 (wt/wt); d) 0.8-1.2 M of lithium hexafluorophosphate in a solvent mixture of ethylene carbonate with ethyl methyl carbonate having the weight ratio 40-60:40-60 (wt/wt); and e) 1.0- 1.4 M of lithium hexafluorophosphate in a solvent mixture of ethylene carbonate with ethyl methyl carbonate having the weight ratio 2.0-4.0:5.0-8.0 (wt/wt) and vinylene carbonate 2% w/w. The electrolyte composition of any one of claims 19 to 29 for use in preparing a cathode electrolyte substrate for increasing a cathode capacity.
The electrolyte composition of any one of claims 19 to 29 for use in preparing an anode electrolyte substrate for increasing an anode capacity. An energy storage device comprising an electrolyte composition of any one of claims 19 to 29 and further comprising: a) A cathode prepared from a composition containing an active material and a binder and coated on a current collector; b) An anode prepared from a composition containing an active material and a binder and coated on a current collector; and c) A separator between the cathode and anode, said separator constitutes an electric insulator allowing ions movement via pores, but blocking an electron flow. The energy storage device of claim 32, wherein the cathode active material is selected from the group consisting of Lithium Nickel Cobalt Manganese Oxide (LiNiCoMnO2), Lithium Iron Phosphate (LiFePO4), Lithium Nickel Manganese Spinel (LiNio.5Mn1.5O4), Lithium Nickel Cobalt Aluminium Oxide (LiNiCoAlO2), Lithium Manganese Oxide (LiMn2O4) and Lithium Cobalt Oxide (LiCoO2). The energy storage device of claim 32 or 33, wherein the anode active material is selected from the group consisting of graphite, SiO2, Si or mixtures thereof. The energy storage device of any one of claims 32 to 34, wherein said energy storage device is selected from a supercapacitor of either an aqueous or organic solvent electrolyte type, nickel/metal hydride battery, lead-acid battery, Li-ion battery, and Li-ion polymer battery. The energy storage device of claim 35, wherein said energy storage device is a Li-ion battery.
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| CN108306013A (en) * | 2017-12-25 | 2018-07-20 | 风帆有限责任公司 | A kind of fast charging and discharging type high power lithium ion cell and production method |
| CN109119634A (en) * | 2018-08-03 | 2019-01-01 | 无锡泰科纳米新材料有限公司 | A kind of new type lithium ion battery graphene conductive agent and preparation method thereof |
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