WO2023239312A1 - Thermoplastic based composite single-layer cathode used in secondary batteries - Google Patents
Thermoplastic based composite single-layer cathode used in secondary batteries Download PDFInfo
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- WO2023239312A1 WO2023239312A1 PCT/TR2022/050563 TR2022050563W WO2023239312A1 WO 2023239312 A1 WO2023239312 A1 WO 2023239312A1 TR 2022050563 W TR2022050563 W TR 2022050563W WO 2023239312 A1 WO2023239312 A1 WO 2023239312A1
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- Prior art keywords
- cathode
- thermoplastic
- weight
- secondary batteries
- based composite
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- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 39
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 239000002356 single layer Substances 0.000 title claims abstract description 14
- -1 cation ions Chemical class 0.000 claims abstract description 15
- 239000012815 thermoplastic material Substances 0.000 claims abstract description 9
- 230000002787 reinforcement Effects 0.000 claims abstract description 8
- 239000000945 filler Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 238000001125 extrusion Methods 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 9
- 150000002902 organometallic compounds Chemical class 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 5
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 5
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 4
- 229920002530 polyetherether ketone Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920001470 polyketone Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 3
- 229920010524 Syndiotactic polystyrene Polymers 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 239000004677 Nylon Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims 3
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims 3
- 229920002223 polystyrene Polymers 0.000 claims 3
- 229920006259 thermoplastic polyimide Polymers 0.000 claims 2
- 229920000265 Polyparaphenylene Polymers 0.000 claims 1
- 239000003623 enhancer Substances 0.000 claims 1
- 229920000915 polyvinyl chloride Polymers 0.000 claims 1
- 238000007493 shaping process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 17
- 229910052782 aluminium Inorganic materials 0.000 abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 5
- 239000010406 cathode material Substances 0.000 description 12
- 238000004146 energy storage Methods 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 230000001965 increasing effect Effects 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 150000001721 carbon Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006182 cathode active material Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000002681 magnesium compounds Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003856 thermoforming Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- HGBJDVIOLUMVIS-UHFFFAOYSA-N [Co]=O.[Na] Chemical compound [Co]=O.[Na] HGBJDVIOLUMVIS-UHFFFAOYSA-N 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- OOIOHEBTXPTBBE-UHFFFAOYSA-N [Na].[Fe] Chemical compound [Na].[Fe] OOIOHEBTXPTBBE-UHFFFAOYSA-N 0.000 description 1
- SWLWKUBAKZNVAR-UHFFFAOYSA-N [O-2].[Mg+2].[Na+] Chemical compound [O-2].[Mg+2].[Na+] SWLWKUBAKZNVAR-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- NDPGDHBNXZOBJS-UHFFFAOYSA-N aluminum lithium cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Al+3].[Co++].[Ni++] NDPGDHBNXZOBJS-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011982 device technology Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- KXNAKBRHZYDSLY-UHFFFAOYSA-N sodium;oxygen(2-);titanium(4+) Chemical compound [O-2].[Na+].[Ti+4] KXNAKBRHZYDSLY-UHFFFAOYSA-N 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
Definitions
- Thermoplastic material is made conductive by adding reinforcement and/or filler elements to electrically insulating thermoplastic polymers for use as cathodes of secondary batteries.
- the cathode source material applied on the traditionally used aluminum sheet it provides the ability to provide electrical conductivity and cation ions without using the aluminum sheet as the cathode host, allowing the use of cathodes containing a single layer of thermoplastic composite material.
- One of the essential basic materials used for energy storage, batteries, are systems used to convert chemical energy into electrical energy.
- the types of batteries commonly used today are primary batteries and secondary batteries.
- Primary batteries are non-rechargeable, secondary batteries are rechargeable.
- the secondary batteries can be recharged and reused, and their sensitivity to the environment enables them to be used more widely.
- An increasing number of research and development projects to develop secondary batteries was carried out on especially lithium-ion (Li-ion) batteries, which stand out in terms of ease of use.
- intensive studies have been conducted on developing new generation composite cathode and anode electrodes with low cost and high efficiency to increase energy efficiency.
- Almost every individual has portable electronic devices (mobile phones, cameras, computers, etc.) in our age. With the effect of technological developments, most of the electronic devices we use in our daily life have become and continue to be suitable for wireless use.
- Li-ion batteries are the most popular secondary batteries in use today. Li-ion batteries use a lithium source (lithium metal, lithium salt, or organolithium compounds) as the cathode element, carbon-based compounds, ceramic or metallic salts as a host anode element, and an anhydrous organic solution or solidphase electrolyte as the electrolyte.
- a lithium source lithium metal, lithium salt, or organolithium compounds
- carbon-based compounds carbon-based compounds
- ceramic or metallic salts as a host anode element
- anhydrous organic solution or solidphase electrolyte as the electrolyte.
- LiCoO2, LiMn2O4 or LiFePO4 Lithium Nickel Manganese Cobalt and Lithium Nickel Cobalt Aluminum Oxide are applied on an aluminum collector and used as a source of lithium ions.
- Sodium sources materials are used such as sodium cobalt oxide, sodium magnesium oxide, sodium iron phosohate, or sodium titanium oxide.
- calcium metal oxides are examples of cathode active materials used in calcium batteries.
- cathode elements used today are Lithium and Sodium, and the chemical structures of these materials, the redox reactions in the battery, and the substances used to form the battery cell by providing these reactions are explained in the article "2021 roadmap for sodium-ion batteries” for sodium batteries and both lithium and sodium Cathode materials created with additives for energy storage were given in the Journal of Power Sources in an article named "Sodium and lithium incorporated cathode materials for energy storage applications - A focused review" in 2021. While the energy storage mechanisms in the anode material are divided into intercalation, conversion reactions, or alloying, cathode materials store energy by intercalation or conversion reactions. The simultaneous application of these mechanisms is an essential building block that directly affects battery efficiency. Each electrode material group has its advantages and limitations.
- the limited specific capacity of the cathode materials is one of the major obstacles for improving the energy densities of existing lithium-ion batteries.
- the production of new secondary batteries with long cycle life and higher energy density is critical to reduce the weight, costs, and environmental impact of portable electronic devices and electric or hybrid vehicles.
- To improve the performance of the cathode material studies have been made to widen the thickness of the shield coating on the cathode surface to a point where it can inhibit oxygen discharge at higher temperatures. It is mentioned in the article "Metal oxide-coated cathode materials for Li-ion batteries-A review,” published in the Journal of Alloys and Compounds in 2019.
- One of the basic principles is that the cathode surface, with a coating of sufficient thickness to facilitate the increase in performance, should be ionic and electrically conductive if it increases cell resistance and adversely affects regular battery operation.
- thermoplastic-based single-layer cathode used in secondary batteries.
- New materials must overcome existing challenges such as high cost, recyclability, reliability, and energy consumption.
- Thermoplastics have become one of the most widely used materials of modern life in recent years, thanks to their superior mechanical properties, thermal stability, workability, and recyclability.
- Thermoplastics are polymers that can be softened and melted by applying heat and processing in the softened state (e.g., thermoforming) or melted (e.g., extrusion and injection molding).
- Thermoplastic polymers can be repeatedly processed by heat and directly recycled to make new products.
- Typical manufacturing processes used to make thermoplastic parts are injection molding, blow molding, and thermoforming.
- thermoplastics have high ductility and impact resistance. They can also be joined by various welding techniques such as resistance welding, vibration welding, and ultrasonic welding. Also, cycle times for thermoplastic parts are pretty low.
- composite materials especially polymer-based composite materials
- Thermoplastic-based composites are gaining increasing attention due to their advantages: lower production cost, high strength, low moisture content, no curing, rework flexibility, and high-temperature resistance.
- Thermoplastic-based composites are obtained by combining organic or inorganic polymers as a matrix and reinforcement, additives, and/or filling materials in a specific ratio.
- thermoplastic materials widely studied and widely used globally, have not been tried before as a cathode tool used for energy storage in secondary batteries.
- thermoplastic-based composite materials are suitable for intercalation reaction due to the molecular structure of thermoplastics and can be a cathode material due to their high charge-discharge capacity.
- thermoplastic-based composite materials are quickly done by the extrusion method. Compared to the current cathode production method, the extrusion method is practical and faster. Also, since thermoplastics are easy to shape, they pave the way for using quickly, various, and more accessible methods during processing after they are produced as cathode material. In addition, the recycling of thermoplastic materials is easier and faster than existing cathode materials.
- thermoplastic-based composite material as the cathode material of secondary batteries are as follows.
- thermoplastic materials cannot be used as electrode cells alone is that plastics are electrical insulators by nature.
- thermoplastic-based composite materials are suitable for electrical conduction and energy storage.
- electrical conductivity, energy storage, and thermal properties are improved by adding metal/metal mineral/organometallic compounds to thermoplastic materials, as well as carbonderived reinforcement and/or filler elements.
- Thermoplastic-based composite material with electrical conductivity and energy storage properties is used as active cathode material in secondary batteries.
- a thermoplastic matrix in polymer-based composite material Polyethylene (PE), Polypropylene (PP), Polystyrene (PS), Polyethylene terephthalate (PET or PTFE), Polyamide (PA) (Nylon), Polyvinyl chloride (PVC), Polycarbonate (PC), Acrylonitrile butadiene styrene (ABS), Polyvinylidene chloride (PVDC), Polybutylene Terephthalate (PBT), Polyphenylene Sulfide (PPS), At least one of the thermoplastic matrix material types such as Syndiotactic Polystyrene (SPS), Polyether ether ketone (PEEK), Polyketones (POK) is used.
- the thermoplasticbased composite recipe is created by adding metal, metal salts (Metal minerals), organometallic compounds, and carbon derivatives (graphite, graphene,
- Twin-screw extruder is used in the production of thermoplastic-based composite material.
- thermoplastic composite material with twin-screw extruder, metal and/or metal salt, organometallic compounds and carbon derivative, primary and secondary antioxidants, compatibilizing side feeders are added into the molten thermoplastic matrix material.
- This molten material is passed through water bath and cut into granules with the help of a pelletizer.
- the main mechanisms involved in an extrusion process are feeding, melting, and homogeneous mixing.
- the ratio of screw length to diameter (L/D ratio) affects the mixing and homogeneity of the output.
- the exit velocity of the material from the extruder depends on the screw speed, barrel temperature, screw configuration, and melt viscosity.
- thermoplastic matrix material is used in the thermoplastic-based composite material produced by the extrusion method.
- These materials are turned into granules or extrudates as a result of the extrusion process.
- thermoplastic-based composite materials of extrudates that are granulated or extruded directly are filmed with a plastic film machine.
- the thickness of these shaped film materials should be in the range of 0.10 - 1.00 mm.
- it should only be added with a binder or by extrusion using additional chemicals, and the single-layer cathode should be ready as a material to be used directly in the battery.
- thermoplastic-based composite material as a cathode in Li-ion batteries, which are one of the secondary batteries, are given below;
- thermoplastic matrix material In order to be a single-layer cathode of thermoplastic-based composite materials, 30 - 80% by weight of thermoplastic matrix material is used. Lithium, Sodium, Calcium, Magnesium compounds and/or derivatives that can be a source of cations at a rate of 20-60% by weight as reinforcement and/or filler, 3-15% by weight of metal and/or 10-30% by weight of metal mineral and/or by weight of It is prepared for the extruder method by using 10-30% organometallic compounds and/or 1-15% by weight binder additives and/or 1-15% by weight conductivity enhancing additives.
- the single-layer cathode is formed into a film and/or sheet form by injection molding directly from the granule, or a flexible structure is gained by drawing the extrudates as films and/or sheets after the direct extrusion process.
- the single-layer cathode material is cut and shaped according to the desired battery type (pen battery, button cell, etc.).
- thermoplastic-based composite material which is the subject of the invention, can be produced in different secondary battery types suitable for all kinds of sectors (for example, automotive, electrical-electronics, defense, aerospace industry, etc.) where energy storage applications are used.
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
For the use of secondary batteries as cathodes, reinforcement and/or filler elements have been added to electrically insulating thermoplastic polymers to make the thermoplastic material conductive. As an alternative to the cathode source material applied on the traditionally used aluminum sheet, it provides the ability to provide electrical conductivity and cation ions without using the aluminum sheet as the cathode host, allowing the use of cathodes containing a single layer of thermoplastic composite material.
Description
THERMOPLASTIC BASED COMPOSITE SINGLE-LAYER CATHODE USED IN SECONDARY BATTERIES
Technical Field
Thermoplastic material is made conductive by adding reinforcement and/or filler elements to electrically insulating thermoplastic polymers for use as cathodes of secondary batteries. As an alternative to the cathode source material applied on the traditionally used aluminum sheet, it provides the ability to provide electrical conductivity and cation ions without using the aluminum sheet as the cathode host, allowing the use of cathodes containing a single layer of thermoplastic composite material.
Prior Art
One of the most critical problems of our age is to find environmentally friendly and low-cost resources in energy production and storage in line with technological developments. In recent years, interest in alternative fuel sources and green energies to replace fossil fuels has increased, and an effort has been made to replace traditional fuel sources. The most critical renewable or sustainable energy sources are solar, wind, and hydroelectric. Due to the inability of renewable energy sources to be continuous or stable, the need for energy storage devices increases day by day after electricity is produced.
One of the essential basic materials used for energy storage, batteries, are systems used to convert chemical energy into electrical energy.
The types of batteries commonly used today are primary batteries and secondary batteries. Primary batteries are non-rechargeable, secondary batteries are rechargeable. The secondary batteries can be recharged and reused, and their sensitivity to the environment enables them to be used more widely. An increasing number of research and development projects to develop secondary batteries was carried out on especially lithium-ion (Li-ion) batteries, which stand out in terms of ease of use. In recent years, intensive studies have been conducted on developing new generation composite cathode and anode electrodes with low cost and high efficiency to increase energy efficiency.
Almost every individual has portable electronic devices (mobile phones, cameras, computers, etc.) in our age. With the effect of technological developments, most of the electronic devices we use in our daily life have become and continue to be suitable for wireless use. It is inevitable that these devices, which have become wireless, need a portable energy source. Features such as having a high energy density, long service life, being able to be charged in a short time, and having minimum damage to the environment are required from this energy source. In this context, rechargeable secondary batteries are widely used for portable electronic device technology, which will meet the energy need.
Li-ion batteries are the most popular secondary batteries in use today. Li-ion batteries use a lithium source (lithium metal, lithium salt, or organolithium compounds) as the cathode element, carbon-based compounds, ceramic or metallic salts as a host anode element, and an anhydrous organic solution or solidphase electrolyte as the electrolyte.
In the cathode elements used in the current art, LiCoO2, LiMn2O4 or LiFePO4, Lithium Nickel Manganese Cobalt and Lithium Nickel Cobalt Aluminum Oxide are applied on an aluminum collector and used as a source of lithium ions. In addition, Sodium sources materials are used such as sodium cobalt oxide, sodium magnesium oxide, sodium iron phosohate, or sodium titanium oxide. Moreover, calcium metal oxides are examples of cathode active materials used in calcium batteries. The most crucial cathode elements used today are Lithium and Sodium, and the chemical structures of these materials, the redox reactions in the battery, and the substances used to form the battery cell by providing these reactions are explained in the article "2021 roadmap for sodium-ion batteries" for sodium batteries and both lithium and sodium Cathode materials created with additives for energy storage were given in the Journal of Power Sources in an article named "Sodium and lithium incorporated cathode materials for energy storage applications - A focused review" in 2021. While the energy storage mechanisms in the anode material are divided into intercalation, conversion reactions, or alloying, cathode materials store energy by intercalation or conversion reactions. The simultaneous application of these mechanisms is an essential building block that directly affects battery efficiency. Each electrode material group has its advantages and limitations. Therefore, selecting suitable electrode materials is the main issue for battery efficiency and applicability. The limited specific capacity of the cathode
materials is one of the major obstacles for improving the energy densities of existing lithium-ion batteries. The production of new secondary batteries with long cycle life and higher energy density is critical to reduce the weight, costs, and environmental impact of portable electronic devices and electric or hybrid vehicles. To improve the performance of the cathode material, studies have been made to widen the thickness of the shield coating on the cathode surface to a point where it can inhibit oxygen discharge at higher temperatures. It is mentioned in the article "Metal oxide-coated cathode materials for Li-ion batteries-A review," published in the Journal of Alloys and Compounds in 2019. One of the basic principles is that the cathode surface, with a coating of sufficient thickness to facilitate the increase in performance, should be ionic and electrically conductive if it increases cell resistance and adversely affects regular battery operation.
In current solution techniques, there is generally a trend towards composite materials containing polymeric composite, ceramic composite, metallic composite, or carbon-derived nanoparticles or reinforcements with known electrical conductivity in line with the articles mentioned above. The desired discharge capacity, energy density, and cycle number gain in the cathode materials are studied in this context. However, problems have been experienced in putting them on the market due to depleted lithium resources, the difficulty of producing alternative raw materials, and the production track's cost.
As a result of the researches, it was concluded that there is no thermoplastic-based single-layer cathode used in secondary batteries.
Purpose of the Invention
It is essential to reduce environmental pollution, meet the demands of the industry and develop materials with excellent properties while designing recyclable and economical materials.
New materials must overcome existing challenges such as high cost, recyclability, reliability, and energy consumption.
Thermoplastics have become one of the most widely used materials of modern life in recent years, thanks to their superior mechanical properties, thermal stability, workability, and recyclability.
Thermoplastics are polymers that can be softened and melted by applying heat and processing in the softened state (e.g., thermoforming) or melted (e.g., extrusion and injection molding). Thermoplastic polymers can be repeatedly processed by heat and directly recycled to make new products. Typical manufacturing processes used to make thermoplastic parts are injection molding, blow molding, and thermoforming.
In addition to the recycling advantage, thermoplastics have high ductility and impact resistance. They can also be joined by various welding techniques such as resistance welding, vibration welding, and ultrasonic welding. Also, cycle times for thermoplastic parts are pretty low.
In recent years, composite materials, especially polymer-based composite materials, have been increasing their popularity in many sectors due to their versatile use, ease of preparation, availability of raw materials, environmental friendliness, improved mechanical properties for desired products, low density, and low cost.
Polymers are often reinforced with other materials to form composites so that the material adequately has the properties required for optimal performance in various fields. Thermoplastic-based composites are gaining increasing attention due to their advantages: lower production cost, high strength, low moisture content, no curing, rework flexibility, and high-temperature resistance. Thermoplastic-based composites are obtained by combining organic or inorganic polymers as a matrix and reinforcement, additives, and/or filling materials in a specific ratio.
It has been concluded that thermoplastic materials, widely studied and widely used globally, have not been tried before as a cathode tool used for energy storage in secondary batteries. As mentioned in the current situation, it is predicted that thermoplastic-based composite materials are suitable for intercalation reaction due to the molecular structure of thermoplastics and can be a cathode material due to their high charge-discharge capacity.
Thermoplastic-based composite materials are quickly done by the extrusion method. Compared to the current cathode production method, the extrusion method is practical and faster. Also, since thermoplastics are easy to shape, they pave the way for using quickly, various, and more accessible methods during
processing after they are produced as cathode material. In addition, the recycling of thermoplastic materials is easier and faster than existing cathode materials.
The advantages of thermoplastic-based composite material as the cathode material of secondary batteries are as follows.
• To improve the functioning of the cathode as a lithium source, increasing the discharge capacity, energy capacity, and number of cycles of the anode,
• To standardize and facilitate the process in the production of the cathode and to reduce production costs,
• To prevent the safety problems of Lithium-ion batteries (explosion, heating, flaming, etc.)
• Recycling,
• Developing the cathode with a new method and providing ease of use with a single-layer structure.
Detailed Description of the Invention
The main reason why thermoplastic materials cannot be used as electrode cells alone is that plastics are electrical insulators by nature. With the studies carried out, thermoplastic-based composite materials are suitable for electrical conduction and energy storage. Within the scope of these studies, electrical conductivity, energy storage, and thermal properties are improved by adding metal/metal mineral/organometallic compounds to thermoplastic materials, as well as carbonderived reinforcement and/or filler elements.
Thermoplastic-based composite material with electrical conductivity and energy storage properties is used as active cathode material in secondary batteries. As a thermoplastic matrix in polymer-based composite material; Polyethylene (PE), Polypropylene (PP), Polystyrene (PS), Polyethylene terephthalate (PET or PTFE), Polyamide (PA) (Nylon), Polyvinyl chloride (PVC), Polycarbonate (PC), Acrylonitrile butadiene styrene (ABS), Polyvinylidene chloride (PVDC), Polybutylene Terephthalate (PBT), Polyphenylene Sulfide (PPS), At least one of the thermoplastic matrix material types such as Syndiotactic Polystyrene (SPS), Polyether ether ketone (PEEK), Polyketones (POK) is used. The thermoplasticbased composite recipe is created by adding metal, metal salts (Metal minerals), organometallic compounds, and carbon derivatives (graphite, graphene, carbon
nanotube, carbon fiber, etc.) materials to electrically insulating polymers to provide conductivity.
Twin-screw extruder is used in the production of thermoplastic-based composite material.
During the production of thermoplastic composite material with twin-screw extruder, metal and/or metal salt, organometallic compounds and carbon derivative, primary and secondary antioxidants, compatibilizing side feeders are added into the molten thermoplastic matrix material. This molten material is passed through water bath and cut into granules with the help of a pelletizer.
The main mechanisms involved in an extrusion process are feeding, melting, and homogeneous mixing. The ratio of screw length to diameter (L/D ratio) affects the mixing and homogeneity of the output. The exit velocity of the material from the extruder depends on the screw speed, barrel temperature, screw configuration, and melt viscosity.
In line with these parameters, 30 - 80% by weight of thermoplastic matrix material is used in the thermoplastic-based composite material produced by the extrusion method. Lithium, Sodium, Calcium, Magnesium compounds and/or derivatives that can be a source of cations at a rate of 20-60% by weight as reinforcement and/or filler, 3-15% by weight of metal and/or 10-30% by weight of metal mineral and/or by weight of It is used with 10-30% organometallic compounds and/or 1-15% by weight binder additives and/or 1-15% by weight conductivity increasing additives. These materials are turned into granules or extrudates as a result of the extrusion process.
Firstly, thermoplastic-based composite materials of extrudates that are granulated or extruded directly are filmed with a plastic film machine. The thickness of these shaped film materials should be in the range of 0.10 - 1.00 mm. Depending on the type of thermoplastic material to be used, it should only be added with a binder or by extrusion using additional chemicals, and the single-layer cathode should be ready as a material to be used directly in the battery.
The steps for the use of thermoplastic-based composite material as a cathode in Li-ion batteries, which are one of the secondary batteries, are given below;
• In order to be a single-layer cathode of thermoplastic-based composite materials, 30 - 80% by weight of thermoplastic matrix material is used.
Lithium, Sodium, Calcium, Magnesium compounds and/or derivatives that can be a source of cations at a rate of 20-60% by weight as reinforcement and/or filler, 3-15% by weight of metal and/or 10-30% by weight of metal mineral and/or by weight of It is prepared for the extruder method by using 10-30% organometallic compounds and/or 1-15% by weight binder additives and/or 1-15% by weight conductivity enhancing additives.
• During the extrusion method, the single-layer cathode is formed into a film and/or sheet form by injection molding directly from the granule, or a flexible structure is gained by drawing the extrudates as films and/or sheets after the direct extrusion process.
• After these processes, the single-layer cathode material is cut and shaped according to the desired battery type (pen battery, button cell, etc.).
• Water and oxygen are removed from the single-layered cathode by keeping it in an inert gas atmosphere in order to remove any moisture that may have remained inside the shaped single-layered cathode, and then the process is completed with the battery closure process.
The thermoplastic-based composite material, which is the subject of the invention, can be produced in different secondary battery types suitable for all kinds of sectors (for example, automotive, electrical-electronics, defense, aerospace industry, etc.) where energy storage applications are used.
Claims
CLAIMS A cathode for use in secondary batteries, consisting of; a. Single layer made of thermoplastic-based composite material comprises b. 30 - 80% by weight of thermoplastic material; c. At least one compound with 20-60% by weight of cation source and/or 3-15% by weight of metal and/or 10-30% by weight of metal mineral and/or 10-30% by weight of organometallic compounds as reinforcement and/or filler element and/or 1-15% by weight of binder additives and/or 1-15% by weight of conductivity-enhancing additives. The production method of a cathode for use in secondary batteries, and its characterizing feature is; a. Gaining a flexible structure of thermoplastic-based composite material, which is turned into granules or extrudate by extrusion, by giving the form of thermoplastic composite film and/or sheet with a thickness of 0.01-1.00 mm, b. Cutting and shaping the single-layer cathode into a film and/or sheet according to the desired battery type, c. Removal of water and oxygen by keeping the single-layer cathodes, which are cut and shaped according to the battery type, in an inert gas atmosphere to be ready for the battery production process, d. Including the process steps of using the single-layer cathode from which water and oxygen are removed as electrode cells for battery production, A cathode in accordance with claim 1, its characterizing feature is; thermoplastic-based cathode is produced by the twin-screw extruder method. A cathode in accordance with claim 1, its characterizing feature is; Twin screw extruder method is used together with thermoplastic composite material, additives, fillers, binders, conductivity enhancers. A cathode in accordance with claim 1, its characterizing feature is; Polyethylene (Polyethylene) (PE), Polypropylene (Polypropylene) (PP), Polystyrene (Polystyrene) (PS), Polyethylene terephthalate (Polyethylene
terephthalate) (PET or PTFE), Polyamide (Polyamide) (PA) (Nylon), Polyvinyl chloride ( Polyvinyl chloride (PVC), Polycarbonate (Polycarbonate) (PC), Acrylonitrile butadiene styrene (Acrylonitrile butadiene styrene) (ABS), Polyvinylidene chloride (Polyvinylidene chloride) (PVDC), Polybutylene Terephthalate (PBT), Polyphenylene Sulfiteactic(PPS), Syndiot It is produced from a thermoplastic material containing at least one of Polystyrene (SPS), Polyether ether ketone (PEEK), Polyketones (POK), Thermoplastic Polyimide (TPI).
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US6645675B1 (en) * | 1999-09-02 | 2003-11-11 | Lithium Power Technologies, Inc. | Solid polymer electrolytes |
WO2016036607A1 (en) * | 2014-09-02 | 2016-03-10 | Graphene 3D Lab Inc. | Electrochemical devices comprising nanoscopic carbon materials made by additive manufacturing |
CN114464813A (en) * | 2022-01-24 | 2022-05-10 | 重庆市紫建新能源有限公司 | Lithium ion battery positive current collector, preparation method and lithium ion battery |
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2022
- 2022-06-09 WO PCT/TR2022/050563 patent/WO2023239312A1/en unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6645675B1 (en) * | 1999-09-02 | 2003-11-11 | Lithium Power Technologies, Inc. | Solid polymer electrolytes |
WO2016036607A1 (en) * | 2014-09-02 | 2016-03-10 | Graphene 3D Lab Inc. | Electrochemical devices comprising nanoscopic carbon materials made by additive manufacturing |
CN114464813A (en) * | 2022-01-24 | 2022-05-10 | 重庆市紫建新能源有限公司 | Lithium ion battery positive current collector, preparation method and lithium ion battery |
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