CA3240520A1 - Improved carbonaceous coating material for battery electrode materials - Google Patents
Improved carbonaceous coating material for battery electrode materials Download PDFInfo
- Publication number
- CA3240520A1 CA3240520A1 CA3240520A CA3240520A CA3240520A1 CA 3240520 A1 CA3240520 A1 CA 3240520A1 CA 3240520 A CA3240520 A CA 3240520A CA 3240520 A CA3240520 A CA 3240520A CA 3240520 A1 CA3240520 A1 CA 3240520A1
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- CA
- Canada
- Prior art keywords
- coating material
- coating
- pitch product
- pitch
- petroleum
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
- C10C3/06—Working-up pitch, asphalt, bitumen by distillation
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Civil Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Structural Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Paints Or Removers (AREA)
Abstract
Description
MATERIALS
TECHNICAL FIELD
[001] The present invention generally relates to a coating material comprising a petroleum-derived pitch product for coating primary particles.
BACKGROUND
However, as the carbon formed at the particle surface contributes less to the reversible capacity of the electrode material compared to the particle core, and as the thickness of the carbon layer also influences the insertion rate of lithium ions into the bulk, thinner coatings are preferred.
This hydrophobicity leads to a further problem in connection with the use of binders in water-based electrode manufacturing processes. In order to solve this problem, EP3177651 (Al) proposes a coating of non-graphitic carbon and subsequent oxidation.
SUMMARY
and between 1.0 and 2.5 at 240 C, wherein visc = melt viscosity (mPa.$) and SPM= softening point Mettler in C.
1.5
DETAILED DESCRIPTION
between 1.8 and 2.5 at 220 C and between 1.5 and 2.1 at 240 C, wherein vise =
melt viscosity (mPa.$) and SPM= Mettler softening point C.
while having a SPM between 110 and 130 C.
Sum (Polycyclic Aromatic Hydrocarbons according to US Environmental Protection Agency (EPA)) of less than 7% by weight, or even less than 5%. A sufficiently low B(a)P
content and/or 16 EPA-PAH Sum results obviously in an improved environmental friendliness compared to pure coal tar derived pitch products.
Alcan, or at least 55% Alcan at Mettler softening points between 110-185 C. As the coating material is converted into carbon during the carbonization process, a sufficiently high coke yield allows avoiding a high porosity in the resulting graphite particles due to fewer volatiles formed during the carbonization process. A subsequent treatment in air at temperatures of 400-1000 C in a fluidized bed or rotary kiln may be used to increase the hydrophilicity of the carbon surface and by that to improve the processing of the carbon-coated electrode material in water-based electrode manufacturing processes. A dense carbon layer may be formed with a morphology that is advantageous for the formation of an efficient solid electrolyte interphase at the electrode particle surface. In addition, the nature and quality of the carbon film formed at the particle surface influences the charge losses as well, besides the electrochemically active electrode surface area being in direct contact with the electrolyte of the battery cell.
surface area reduction of at least 40 % at a pitch amount of 5 wt.% for spherical natural graphite with a BET SSA of 6 m2/g and an average particle size of 15 micron used as electrode material in the electrode. The coulombic efficiency of the coated natural graphite (BET 3 m2/g) may increase above 90 %.
5 [0059] In addition, a process in accordance with the present invention gives a high level of reliability by reaching the required softening point and viscosity of the pitch product at lower temperatures compared to conventional ambient pressure distillation and hence leads to better plant reliability. The lower distillation temperatures used in the vacuum distillation process avoid degradation reactions like mesophase and coke formation, leading to fouling of the plant 10 and regular shutdowns.
[0060] Further, the process of the present invention may result in a pitch product with high quality and reliability showing sufficiently high coking value and low 16 EPA
PAH content at low viscosity for use in battery electrodes. 16 EPA PAH level of the resulting binder is lower than of the pure coal tar-derived products giving rise to more environmentally friendly materials.
EXAMPLE 1-6:
[0061] Below Table 1 shows examples of petroleum-derived pitch products and properties comprised in a coating material in accordance with an embodiment of the present invention.
Table 1 Pitch Product Example Example Example Example 4 Example Example Parameter 1 2 3 5 SP, Mettler 120 149.3 152.2 180.2 185 152.3 in C
TI 8 0.7 13.9 18.8 1.3 15.5 in wt.%
01 <1 <0.1 <0.1 0.5 <0.1 0.2 in wt.%
Beta-resin <8 0.7 13.9 18.3 1.3 15.3 in wt. %
Coke value, ALCAN 42 40.9 44.6 58.8 45.7 47.9 in wt.%
Ash <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 in wt.%
B[a]P Content 1530 896 935 931 638 in ppm 16 EPA-PAH sum in 4 1.63 2.25 0.99 0.65 1.59 wt.%
Asphaltenes (SARA) 81.8 76 79.8 95.1 90.7 n.a.
in wt %
Resins (SARA) 11.4 19.3 15.8 3.7 6.4 n.a.
in wt.%
Flash point (small 220-230 240-250 230-240 280-290 285-295 n.a.
scale) in C
Melt viscosity (visc) in mPa s Melt viscosity index -220 C 2.04 2.14 2.27 2.23 2.44 2.16 -240 C 1.75 1.81 1.92 1.89 2.05 1.82 [0062] Table 2 further illustrates the performance of coated natural graphite materials obtained by coating with coating materials consisting of the pitch products of examples 3 and 4 and subsequent carbonization at 1100 C:
Table 2:
Properties carbon- Example 3 Example 4 coated natural graphite BET SSA
in m2 g1 at carbon amount 0% 6.0 6.0 5% 3.0 2.5 7%
2.6 2.0 8% 2.3 Coulombic efficiency 1 St charge/discharge in %
at carbon amount 5 %
90.5 92.4 7%
94.5 94.3 [0063] Below table provides an overview of analytical procedures of the product parameters as used in this text:
Analysis Unit Norm/Method Softening point, Mettler (SPM) C ASTM D3104 Quinoline insoluble matter, 01 % (by weight) DIN 51921 Toluene insoluble matter, TI % (by weight) DIN 51906 Beta-resins % (by weight) Calculation TI-QI
Coke yield (value), Alcan % (by weight) ASTM D4715 Ash (900 C) % (by weight) ASTM D2415 Benzo[a]pyrene content ppm ISO 18287 16 EPA-PAH sum % (by weight) ISO 18287 Flash point (small scale C ISO 3679 equilibrium) Dynamic melt viscosity mPa = s ASTM D5018 measured at temperatures of 160 C, 180 C, 200 C, 220 C, 240 C, 260 C, 280 C
SARA (final product) ASTM D2007 -asphaltenes % (by weight) -resins % (by weight) BET Specific Surface Area m2 g-1 ISO 9277, ASTM C1069 (BET SSA) [0064] EXAMPLE 7:
- Preparation of coated natural graphite samples:
Spherical natural graphite was mixed in an intensive mixer at room temperature for 5 min with pitch powder obtained from petroleum-derived pitch product as described throughout this text and ground to an average particle size of ca. 3-5 lam. The mixture was heat-treated in a nitrogen atmosphere at 110000 for 5 h, with a heat up rate of 100 C/h.
- Electrochemical tests of the carbon-coated natural graphite materials:
The graphite samples were dispersed in a solution of carboxymethyl cellulose (CMC) in water and then the SBR latex binder material was added to achieve a final composition of 96 wt.% graphite, 2 wt.% CMC, and 2 wt.% SBR. The aqueous slurry was deposited on a copper foil by a doctor blade method and the resulting coated foil was dried at 120 C. The dried sheet was roll-pressed and the final electrodes of 17 mm in diameter then were punched out of the sheet. The electrodes having a mass loading of ca. 8.5 mg/cm2, a density of ca. 1.65 g/cm3 and a thickness of ca. 70 rin were vacuum dried at 100 C and tested in lithium coin-half cells using a 1 M
LiPFA EC/DEC (1:1 by weight) electrolyte and a porous polypropylene separator. The first cycle coulombic efficiency and reversible specific charge of the electrode were measured by discharging the half-cell at 0.1 C to 5 mV versus Li/Li+ and keeping the cell at this potential until the current decreased to 0.7 mA, then the cell was charged to 1.5 V vs. Li/Li+ and kept at this potential until the cell current dropped to 0.7 mA. The coulombic efficiency of the first charge/discharge cycle was calculated from the reversible specific charge/(reversible specific charge + irreversible specific charge) =
measured mAh (18' cycle charge)/measured mAh (V cycle discharge) in percent.
Claims (18)
while having a SPM between 140 and 160 C.
weight.
by weight.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP21214111.3 | 2021-12-13 | ||
| EP21214111.3A EP4194396A1 (en) | 2021-12-13 | 2021-12-13 | Improved carbonaceous coating for battery electrode materials |
| PCT/EP2022/085668 WO2023110903A1 (en) | 2021-12-13 | 2022-12-13 | Improved carbonaceous coating material for battery electrode materials |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA3240520A1 true CA3240520A1 (en) | 2023-06-22 |
Family
ID=78844833
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA3240520A Pending CA3240520A1 (en) | 2021-12-13 | 2022-12-13 | Improved carbonaceous coating material for battery electrode materials |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20250051647A1 (en) |
| EP (2) | EP4194396A1 (en) |
| JP (1) | JP2024546255A (en) |
| KR (1) | KR20240130718A (en) |
| CN (1) | CN118984806A (en) |
| CA (1) | CA3240520A1 (en) |
| WO (1) | WO2023110903A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4497804A1 (en) * | 2023-07-24 | 2025-01-29 | Rain Carbon bv | Improved thermoplastic carbon precursor material for application in coating, binding, and impregnation processes for the manufacturing of electrodes for steel and aluminium production and batteries |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7033485B2 (en) * | 2001-05-11 | 2006-04-25 | Koppers Industries Of Delaware, Inc. | Coal tar and hydrocarbon mixture pitch production using a high efficiency evaporative distillation process |
| JP2004047350A (en) * | 2002-07-15 | 2004-02-12 | Nippon Carbon Co Ltd | Anode material for high-performance lithium ion secondary battery and method for producing the same |
| KR102405453B1 (en) | 2014-07-15 | 2022-06-03 | 이머리스 그래파이트 앤드 카본 스위춰랜드 리미티드 | Hydrophilic surface-modified carbonaceous particulate material |
| CN106531979A (en) * | 2015-11-16 | 2017-03-22 | 上海杉杉科技有限公司 | Preparation method of high-rate-performance anode material for lithium ion battery |
| CN111232971B (en) * | 2020-01-17 | 2021-10-15 | 广东东岛新能源股份有限公司 | A kind of long-cycle natural graphite-based modified composite material and its preparation method and application |
-
2021
- 2021-12-13 EP EP21214111.3A patent/EP4194396A1/en not_active Withdrawn
-
2022
- 2022-12-13 JP JP2024534700A patent/JP2024546255A/en active Pending
- 2022-12-13 US US18/718,924 patent/US20250051647A1/en active Pending
- 2022-12-13 WO PCT/EP2022/085668 patent/WO2023110903A1/en not_active Ceased
- 2022-12-13 EP EP22836118.4A patent/EP4448448A1/en active Pending
- 2022-12-13 KR KR1020247023359A patent/KR20240130718A/en active Pending
- 2022-12-13 CN CN202280091101.7A patent/CN118984806A/en active Pending
- 2022-12-13 CA CA3240520A patent/CA3240520A1/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JP2024546255A (en) | 2024-12-19 |
| EP4194396A1 (en) | 2023-06-14 |
| CN118984806A (en) | 2024-11-19 |
| KR20240130718A (en) | 2024-08-29 |
| US20250051647A1 (en) | 2025-02-13 |
| EP4448448A1 (en) | 2024-10-23 |
| WO2023110903A1 (en) | 2023-06-22 |
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