CA3136362A1 - Polyvinyl pyrollidone as a dispersant for lithium ion battery cathode production - Google Patents
Polyvinyl pyrollidone as a dispersant for lithium ion battery cathode production Download PDFInfo
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- CA3136362A1 CA3136362A1 CA3136362A CA3136362A CA3136362A1 CA 3136362 A1 CA3136362 A1 CA 3136362A1 CA 3136362 A CA3136362 A CA 3136362A CA 3136362 A CA3136362 A CA 3136362A CA 3136362 A1 CA3136362 A1 CA 3136362A1
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- solvent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
-
- 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
-
- 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
-
- 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
- H01M4/623—Binders being polymers fluorinated polymers
-
- 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)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
CATHODE PRODUCTION
FIELD
[0001] This invention relates to the production of lithium ion batteries.
In one aspect the invention relates to the production of the cathode of such batteries while in another aspect, the invention relates to the materials used in the production of such cathodes.
BACKGROUND
Nano-size particles are well known to have a very high surface area and surface energy but because of these properties, they aggregate easily or, in other words, they are difficult to disperse. If the nano-size conductive agent particles are not well dispersed within the cathode, then their boost to cathode conductivity is muted.
[0006] In one embodiment the present disclosure provides a process of making a lithium ion battery cathode, the process comprising the step of forming a slurry of an active material, a nano-size conductive agent, a binder polymer, a solvent and a dispersant,
BRIEF DESCRIPTION OF THE DRAWINGS
conductive carbon black in different dispersants.
DETAILED DESCRIPTION
Definitions
The term "or," unless stated otherwise, refers to the listed members individually as well as in any combination. Use of the singular includes use of the plural and vice versa.
In the context of the anode of a lithium ion cell, the active material is the receptor of the lithium ions, e.g., graphite. The active materials are typically in the form of very small particles having a diameter from 1000 nanometers to 100 micrometers.
Nonlimiting examples of suitable alkyl groups include, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl (or 2-methylpropyl), etc. In one embodiment, the alkyls have 1 to 20 carbon atoms.
The cathode is the electrode where reduction takes place within the battery during discharge.
Production Process for Lithium Ion Battery
Active materials include but are not limited to lithium cobalt oxide (LiCo02), lithium manganese oxide (LiMn204), lithium nickel manganese cobalt oxide (LiNiMnCo02 or NMC), lithium iron phosphate (LiFePO4), lithium nickel cobalt aluminum oxide (LiNiCoA102), and lithium titanate (Li4Ti5012). The slurry is then coated onto a foil, typically aluminum for the cathode and copper for the anode, and the coated foil then dried.
The dried foil is then calendared in a calendar machine, allowed to set, and then collected on a reel. Eventually the cathode and anode films are combined into an electrode stack and the cell is completed with the addition of electrolyte.
Conductive Agent
P conductive carbon black available from TIIVICALI'm Graphite and Carbon is an example of a commercially available conductive agent that can be used in the practice of embodiments of this disclosure. SUPER P conductive carbon black has a mean particle size of approximately 1 micron.
Dispersant
( in which n is from 100 to 10,000. In some embodiments, n in the above structure is from 300 to 3,000. The dispersant can be a single PVP species, e.g., of one molecular weight, or a mixture of PVPs differing in molecular weight. The PVP has a molecular weight of 3,000 to 400,000 in some embodiments, 10,000 to 200,000 in other embodiments, and 30,000 to 60,000 in other embodiments. Non-limiting examples of commercially available PVP
include PVP
K-15, PVP K-30, PVP K-60 and others which are commercially available from a variety of suppliers. In some embodiments where the solvent used in the slurry is DMPA, the amount of PVP in the slurry can be 0.01 to 5 weight percent, or 0.1 to 2 weight percent, or 0.3 to 1 weight percent (each based on the total weight of the slurry).
typically comprises at least 50, or 55, or 60, or 65, or 70, or 75, wt% of the dispersant mixture.
In some embodiments where other dispersants are used with PVP, the mixture of dispersants does not include ethyl cellulose. In some embodiments where other dispersants are used with PVP, the mixture of dispersants comprises less than 1 wt% ethyl cellulose, or less than 0.1 wt% ethyl cellulose, or less than 0.01 wt% ethyl cellulose (each based on the weight of the dispersant mixture).
Solvents
diethylpropionamide;
N,N dipropylpropionamide; N,N dibutylpropionamide; N,N
dimethylethylpropionamide; 3-butoxy-N-methyl propionamide; and N,N-diethyl acetamide (DEAC). In one embodiment the compound of Formula 1 is DMPA.
Examples of solvents that can be blended with the solvent according to Formula 1 include N,N-dimethylacetoacetamide (DMAA), N,N-diethylacetoacetamide (DEAA), y-valerolactone, triethyl phosphate (TEP), and mixtures thereof.
in the production process for lithium ion batteries. As such, they are used in the same manner as NMP in such processes (e.g. such as the process shown in Figure 1). Typically, this process includes the steps of dissolving the binder polymer with the solvent, and then forming a slurry from the dissolved binder, an active material, a conductive agent and a dispersant. The slurry is then applied to a foil, and the foil dried during which the solvent is removed by evaporation.
EXAMPLES
Materials
dehydrated molecular sieve (from Sigma-Aldrich) for more than 2 days to remove water.
Ltd. The dispersants are dehydrated in a 60 C oven for at least two hours prior to use.
The PVDF is dehydrated in a 80 C oven for at least two hours prior to use.
Example 1
solvent are measured. 0.2 grams of the specified dispersant and 19.8 grams of DMPA are added in a vial which is then sealed with a cap. The vial is secured in a SPEEDMDCI'm DAC
150.1 FVZ-k mixer and mixed at 2000 rpm. During mixing, this mixer is stopped every 2 minutes for cooling and to determine if all of the dispersant has dissolved. The time at which all of the dispersant in the vial has dissolved is recorded. The different samples and the results are shown in Table 1.
Table 1 Sample Composition Time to Dissolve (minutes) Comparative Example A 1 wt. % ethyl cellulose in 28 DMPA
Comparative Example B 2 wt. % ethyl cellulose in 52 DMPA
Comparative Example C 3 wt. % ethyl cellulose in 66 DMPA
Inventive Example 1 1 wt. % PVP in DMPA 4 Inventive Example 2 2 wt. % PVP in DMPA 6 Inventive Example 3 3 wt. % PVP in DMPA 8
Comparative Example A generated a stable foam (having a height of less than 1 centimeter) which lasted for more than 30 minutes. In contrast, Inventive Example 1 did not generate a foam bubble even after vigorous shaking.
Example 2
The specified amount of conductive agent (Super P conductive carbon black) is weighed in a vial. The solvent with the specified dispersant dissolved therein is added.
The vial is sealed with a cap and mixed in a SPEEDMDCI'm DAC 150.1 FVZ-k mixer at 3000 rpm for 3 minutes, and then repeated for another 3 minutes. After mixing, the conductive agent dispersion is cast on a slide glass to observe if the conductive agent particles are agglomerated or dispersed. A LEICA DM2500 M microscope is used to observe the appearance of the solution and take micrographs. Figure 2 shows the appearance of the conductive agent in two dispersants at different concentrations. As shown in Figure 2, the conductive agent disperses a little better in DMPA when PVP is used as a dispersant relative to using ethyl cellulose as a dispersant.
Example 3
Each slurry formulation is prepared as follows.
During this step, the mixer is stopped every 3 minutes for cooling. The viscosity of each cathode slurry is measured at 25 C according to ASTM D562-2001 using a #63 spindle on a Brookfield DV1MLVTJO viscometer. The viscosities are shown in Table 2.
The temperature is then increased by 10 C and held at that temperature for 30 minutes. These increases continue until a temperature of 100 C is reached.
total of twelve data points are collected, and the average electric resistance is reported in Table 2. In addition, two spots on four different samples of each cathode slurry formulation are tested for adhesion. The adhesion is measured in accordance with ASTM D-3359. These results are shown in Table 2.
Table 2 Comparative Comparative Inventive Inventive Example D Example E Example 4 Example 5 Cathode Cathode Material slurry (LFP) 56.93% 56.98% 56.93% 56.98%
formulation Conductive Agent (Super P Carbon Black) 1.20% 1.20% 1.20% 1.20%
Dispersant 1 (ethyl cellulose) 0.12% 0.04% / /
Dispersant 2 (PVP) / / 0.12% 0.04%
Binder (PVDF) 1.80% 1.80% 1.80% 1.80%
Solvent (DMPA) 39.95% 39.98% 39.95% 39.98%
Total 100.00% 100.00% 100.00% 100.00%
Cathode slurry viscosity (cP) 6983 6967 6887 6873 Cathode coating thickness (um) 50.3 51.2 50.8 50.3 Cathode coating electric resistance (Ohm) 104.8 93.6 94.2 95.7 Cathode coating adhesion (ASTM- 4B 4B 4B 4B
dissolves much more quickly in the solvent relative to ethyl cellulose dispersant while also avoiding foaming. This is beneficial for the manufacture of lithium ion batteries.
Claims (10)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2019/084562 WO2020215316A1 (en) | 2019-04-26 | 2019-04-26 | Polyvinyl pyrollidone as a dispersant for lithium ion battery cathode production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA3136362A1 true CA3136362A1 (en) | 2020-10-29 |
Family
ID=72941465
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA3136362A Pending CA3136362A1 (en) | 2019-04-26 | 2019-04-26 | Polyvinyl pyrollidone as a dispersant for lithium ion battery cathode production |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20220376260A1 (en) |
| EP (1) | EP3959765A4 (en) |
| JP (1) | JP7349508B2 (en) |
| CN (1) | CN113614959B (en) |
| BR (1) | BR112021018887A2 (en) |
| CA (1) | CA3136362A1 (en) |
| WO (1) | WO2020215316A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4060780B1 (en) * | 2021-03-15 | 2023-07-26 | Evonik Operations GmbH | Dispersion and coating composition containing lithium metal phosphate |
| WO2023136218A1 (en) * | 2022-01-17 | 2023-07-20 | ダイキン工業株式会社 | Composition, electrode, and secondary battery |
| JP7565475B1 (en) * | 2023-03-27 | 2024-10-10 | 関西ペイント株式会社 | Method for producing carbon nanotube dispersion paste and method for producing composite paste for lithium ion secondary batteries |
| WO2025086184A1 (en) * | 2023-10-26 | 2025-05-01 | Dow Global Technologies Llc | Dispersants for cathode slurries with lithium iron phosphate |
| CN117343096B (en) * | 2023-12-04 | 2024-04-02 | 瑞浦兰钧能源股份有限公司 | An ionized conductive agent and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003297356A (en) * | 2002-04-02 | 2003-10-17 | Toyota Central Res & Dev Lab Inc | Positive electrode mixture slurry for lithium secondary battery, positive electrode for lithium secondary battery and lithium secondary battery using the same |
| JP2005121863A (en) * | 2003-10-16 | 2005-05-12 | Fuji Photo Film Co Ltd | Image recording material |
| CN1797825A (en) * | 2004-12-30 | 2006-07-05 | 比亚迪股份有限公司 | Battery of lithium ion, and electrodes of the battery, and their preparation method |
| CN101207193B (en) * | 2006-12-21 | 2010-11-17 | 比亚迪股份有限公司 | A kind of preparation method of electrode slurry |
| CN101207204A (en) * | 2006-12-22 | 2008-06-25 | 比亚迪股份有限公司 | Lithium-ion battery positive electrode material and positive electrode and lithium-ion battery containing the material |
| CN101604767A (en) * | 2008-06-13 | 2009-12-16 | 三星Sdi株式会社 | Electrode assembly and secondary battery including the electrode assembly |
| KR20100044087A (en) * | 2008-10-20 | 2010-04-29 | 삼성전자주식회사 | Electrode composition for inkjet print, electrode and secondary battery prepared using the same |
| CN101752548B (en) * | 2008-12-09 | 2012-09-26 | 比亚迪股份有限公司 | Conductive agent dispersion liquid, electrode slurry, electrode, battery, and preparation methods thereof |
| JP2012009227A (en) * | 2010-06-23 | 2012-01-12 | Toyota Motor Corp | Method of manufacturing lithium ion secondary battery |
| WO2013085509A1 (en) * | 2011-12-07 | 2013-06-13 | CNano Technology Limited | Electrode composition for li ion battery |
| WO2013088929A1 (en) * | 2011-12-16 | 2013-06-20 | 日本電気株式会社 | Secondary battery |
| DE102013213273A1 (en) * | 2013-02-22 | 2014-08-28 | Bayer Materialscience Aktiengesellschaft | Carbon nanotube-containing dispersion and its use in the manufacture of electrodes |
| KR20140110641A (en) * | 2013-03-08 | 2014-09-17 | 삼성에스디아이 주식회사 | Binder composition for electrode, Electrode for a secondary battery and a secondary battery including the same |
| KR20160098370A (en) * | 2014-01-14 | 2016-08-18 | 쇼와 덴코 가부시키가이샤 | Lithium secondary battery and conductive assistant used in same |
| JP5861896B2 (en) * | 2014-03-10 | 2016-02-16 | 株式会社豊田自動織機 | A composition comprising a first positive electrode active material, a second positive electrode active material, a dispersant and a solvent |
| KR102237824B1 (en) * | 2014-07-11 | 2021-04-08 | 삼성전자주식회사 | Air electrode, lithium air battery comprising air electrode, and preparation method thereof |
| JP2016035814A (en) * | 2014-08-01 | 2016-03-17 | 株式会社日本触媒 | Method for manufacturing slurry |
| JP6720488B2 (en) * | 2015-09-08 | 2020-07-08 | 株式会社豊田自動織機 | Method for producing a composition containing a plurality of positive electrode active materials, a conductive auxiliary agent, a binder and a solvent |
| WO2017222895A1 (en) * | 2016-06-23 | 2017-12-28 | Government Of The United States As Represented By The Secretary Of The Air Force | Bendable creasable, and printable batteries with enhanced safety and high temperature stability - methods of fabrication, and methods of using the same |
| CN106299379B (en) * | 2016-10-28 | 2019-02-05 | 合肥国轩高科动力能源有限公司 | A lithium battery positive electrode slurry solvent and preparation method of lithium battery positive electrode slurry using the solvent |
| CN111066192B (en) * | 2017-08-10 | 2026-03-03 | 三菱化学株式会社 | Nonaqueous electrolyte secondary battery |
| CN107946561B (en) * | 2017-11-13 | 2025-09-19 | 深圳市比克动力电池有限公司 | Negative electrode material, preparation method thereof, negative electrode plate and lithium ion battery |
| CN108767235B (en) * | 2018-06-04 | 2020-05-29 | 广州天赐高新材料股份有限公司 | Lithium secondary battery anode slurry and preparation method and application thereof |
| CN109378477A (en) * | 2018-10-11 | 2019-02-22 | 昆山瑞柏电子材料有限公司 | Anode material of lithium battery |
| WO2021002369A1 (en) * | 2019-07-01 | 2021-01-07 | ダイキン工業株式会社 | Composition for electrochemical device, positive electrode mixture, positive electrode structure, and secondary battery |
-
2019
- 2019-04-26 WO PCT/CN2019/084562 patent/WO2020215316A1/en not_active Ceased
- 2019-04-26 US US17/432,414 patent/US20220376260A1/en not_active Abandoned
- 2019-04-26 CA CA3136362A patent/CA3136362A1/en active Pending
- 2019-04-26 BR BR112021018887A patent/BR112021018887A2/en active Search and Examination
- 2019-04-26 CN CN201980094497.9A patent/CN113614959B/en active Active
- 2019-04-26 JP JP2021560843A patent/JP7349508B2/en active Active
- 2019-04-26 EP EP19926665.1A patent/EP3959765A4/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| EP3959765A1 (en) | 2022-03-02 |
| CN113614959A (en) | 2021-11-05 |
| CN113614959B (en) | 2024-10-25 |
| BR112021018887A2 (en) | 2021-11-30 |
| WO2020215316A1 (en) | 2020-10-29 |
| EP3959765A4 (en) | 2023-03-08 |
| JP7349508B2 (en) | 2023-09-22 |
| US20220376260A1 (en) | 2022-11-24 |
| JP2022536580A (en) | 2022-08-18 |
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