WO2024173584A2 - Conducteur de charge polymère - Google Patents

Conducteur de charge polymère Download PDF

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Publication number
WO2024173584A2
WO2024173584A2 PCT/US2024/015840 US2024015840W WO2024173584A2 WO 2024173584 A2 WO2024173584 A2 WO 2024173584A2 US 2024015840 W US2024015840 W US 2024015840W WO 2024173584 A2 WO2024173584 A2 WO 2024173584A2
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value
polymer
pva
chemical structure
naoh
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WO2024173584A3 (fr
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Gao Liu
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University of California Berkeley
University of California San Diego UCSD
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University of California Berkeley
University of California San Diego UCSD
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/125—Intrinsically conductive polymers comprising aliphatic main chains, e.g. polyactylenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment

Definitions

  • This invention relates generally to polymers.
  • the present invention provides for a polymer capable of conductance.
  • the polymer is useful in the manufacture of an electrical or electronic device, such as a battery.
  • the present invention provides for a method of forming a conductive polymer, comprising (a) providing a polyvinyl polymer having the following chemical structure: wherein A is -OH, -OR, F, Cl, Br, I, -SO 4 R, -SO 3 R, -NH2, -NHR, -
  • NR1R2 a phenyl, or a phenyl derivative
  • R, Ri, and/or R2 are each independently an
  • the present invention provides for a method of forming a conductive polymer, comprising (a) providing a precursor polymer having the following chemical structure: wherein A is -OH, -OR, F, Cl, Br, I, -SO 4 R, -SO3R, -NH2, -NHR, -NR1R2, a phenyl, or a phenyl derivative, and R, Ri, and/or R2 are each independently an organic substituent; and (b) heating the precursor polymer thereby forming at least one
  • the present invention provides for a method of forming a conductive polymer, comprising (a) providing a precursor polymer having the following chemical structure: wherein A and A’ are each independently -OH, -OR, F, Cl, Br, I, -SO4R, -SO3R, -NH2, -NHR, -NR1R2, a phenyl, or a phenyl derivative, and R, Ri, and/or R2 are each independently an organic substituent; and (b) heating the precursor polymer thereby forming at least one to form the following chemical structure:
  • the present invention provides for a method of forming a conductive polymer, comprising (a) providing a precursor polymer having the following chemical structure: wherein A, A’, and A” are each independently
  • n has a value of 0 ⁇ n ⁇ 1
  • m has a value of 0 ⁇ m ⁇ 1
  • n + m 1
  • q has a value of 0 ⁇ q ⁇ n
  • p’ has a value of 0 ⁇ p’ ⁇ m
  • q’ has a value of 0
  • p has a value of 0 ⁇ p ⁇ 0.9 and q has a value of 0.1 ⁇ q ⁇ 1. In some embodiments, p has a value of 0 ⁇ p ⁇ 0.8 and q has a value of 0.2 ⁇ q ⁇ 1. In some embodiments, p has a value of 0 ⁇ p ⁇ 0.7 and q has a value of 0.3 ⁇ q ⁇ 1. In some embodiments, p has a value of 0 ⁇ p ⁇ 0.6 and q has a value of 0.4 ⁇ q ⁇ 1.
  • p has a value of 0 ⁇ p ⁇ 0.5 and q has a value of 0.5 ⁇ q ⁇ 1. In some embodiments, p has a value of 0 ⁇ p ⁇ 0.4 and q has a value of 0.6 ⁇ q ⁇ 1. In some embodiments, p has a value of 0 ⁇ p ⁇ 0.3 and q has a value of 0.7 ⁇ q ⁇ 1. In some
  • p has a value of 0 ⁇ p ⁇ 0.2 and q has a value of 0.8 ⁇ q ⁇ 1. In some embodiments, p has a value of 0 ⁇ p ⁇ 0.1 and q has a value of 0.9 ⁇ q ⁇ 1. In some embodiments, p is 0 and q is 1.
  • n is about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or less than 100%, or a percentage within a range of any two preceding percentages
  • m is about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or less than 100%, or a percentage within a range of any two preceding percentages.
  • n is about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or less than 100%, or a percentage within a range of any two preceding percentages
  • m is about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or less than 100%, or a percentage within a range of any two preceding percentages.
  • p is about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or less than 100% of n, or a percentage within a range of any two preceding percentages
  • q is about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or less than 100% of n, or a percentage within a range of any two preceding percentages.
  • p’ is about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or less than 100% of m, or a percentage within a range of any two preceding percentages
  • q’ is about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or less than 100% of m, or a percentage within a range of any two preceding percentages.
  • the method further comprises adding an acid or base to the polyvinyl polymer to form a mixture prior to the heating step (b).
  • the acid or base added to the polyvinyl polymer is 0.0001% to 99.9% by weight of the mixture.
  • the base is a base listed in Table 1.
  • the method comprises adding a base to the polyvinyl polymer to form a mixture prior to the heating step (b), wherein the base is LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH) 2 , Ca(OH) 2 , Sr(OH) 2 , Ba(OH) 2 , or a mixture thereof.
  • the acid is an acid listed in Table 2.
  • the method comprises adding an acid to the polyvinyl polymer to form a mixture prior to the heating step (b), wherein the acid is H 2 SO4, H3PO4, HNO3, HC1, HBr, HI, HPF 6 , HTFSI. HF SI, NC1O 4 , HBrO 4 , HIO 4 , or a mixture thereof.
  • the method further comprises doping the polymer having the chemical structure of (I-b), (Il-b), (Ill-b), or (IV-b) with O2, h, PF&', or like anion, and/or metal cation, to further enhance electronic conductivity.
  • the metal cation is an alkali metal or alkaline earth metal cation.
  • the alkali metal cation is lithium ion, sodium ion, potassium ion, rubidium ion, caesium ion, or the like.
  • the alkaline earth metal cation is beryllium ion, magnesium ion, calcium ion, strontium ion, barium ion, or the like.
  • the chemical structure (I-b), (Il-b), (Ill-b), (IV-b), or a mixture thereof is in a thin film.
  • the method comprises passing an electric current through chemical structure (I-b), (Il-b), (Ill-b), (IV-b), or a mixture thereof.
  • the present invention provides for an electrically conductive composition
  • an electrically conductive composition comprising one or more polymers, wherein each polymer has the chemical structure of (I-b), (Il-b), (Ill-b), (IV-b), or a mixture thereof.
  • the present invention provides for an electric device comprising an electric circuit comprising the composition a chemical structure of (I-b), (Il-b), (Ill-b), (IV-b), or a mixture thereof, wherein an electric current is pass through the chemical structure of (I-b), (Il-b), (III- b), (IV-b), or a mixture thereof.
  • the one or more polymers are electrode binders with electrode materials.
  • the conductive polymers are used as conductive electrode binders with electrode materials to form electrode for battery applications.
  • Fig. 1 From polybutadiene to synthesize polyhydroxybutadiene to thermal formation of polyacetylene
  • Fig. 3 From polybutadiene-cyclohexene to synthesize polyhydroxybutadienecyclodihydroxyhexene to thermal formation of polyacetylene-phenylene
  • Fig. 4 When the depolymerization and decomposition are controlled, the thermal treatment of “polyvinyl A” leads to formation of polyacetylene conductive polymer.
  • R, Ri, R2 can be any organic groups.
  • Fig. 5 Partial elimination of HA of “polyvinyl A” leads to formation of polyacetylene conductive polymer with functional A groups in the polymer structure.
  • R, Ri, R2 can be any organic groups.
  • a base or acid can be added to the polyvinyl A, before heating process. The added acid or base can facilitate lower temperature HA elimination, and prevent polymer from structure decomposition.
  • the added acid or base among ranging from 0.0001% to 99.9% by weight to the polyvinyl A mixture.
  • Base choices LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH) 2 , Ca(OH) 2 , Sr(OH) 2 , Ba(OH) 2 , ammonia (NH3 or NH4.0H), amines and its derivatives such as triethylamine, and nitrogen based organic base such as l,5-Diazabicyclo(4.3.0)non-5-ene (DBN), etc., both strong and weak bases.
  • Acid choices H2SO4, H3PO4, HNO3, HC1, HBr, HI, HPF 6 , HTFSI, HFSI, HC1O 4 , HBrO 4 , HIO4, Acetic acid (HAC), citric acid (CeHsO?), H2SO3, HF, H2S, etc., both strong and week acids.
  • R, Ri, R2 can be any organic groups.
  • Fig. 7 Polyvinyl alcohol partial elimination of H2O without decomposition lead to higher remaining weight. Weight remaining > 59.1%. Partial elimination of OH group of polyvinyl alcohol leads to formation of polyacetylene conductive polymer with functional OH groups in the polymer structure. This OH groups can provide functions such as adhesion or enhance mechanical strength. Fig. 8. Polyvinyl alcohol partial elimination of H2O without
  • SUBSTITUTE SHEET (RULE 26) SUBSTITUTE SPECIFICATION - CLEAN COPY decomposition lead to higher remaining weight. Weight remaining > 59.1%.
  • a base or acid can be mixed to the polyvinyl alcohol, before heating process.
  • the added acid or base can facilitate lower temperature H2O elimination, and prevent polymer chain from structure decomposition.
  • the added acid or base among ranging from 0.0001% to 99.9% by weight to the polyvinyl alcohol mixture.
  • the thermal treatment can be done in ambient air condition, or inert atmosphere such as N2 and Ar gas environment or in reduced pressure to vacuum.
  • inert atmosphere such as N2 and Ar gas environment
  • some remaining hydroxyl groups can also be oxidized to carbonyl groups to adjust the bandgap of the pi-pi conjugation to promote more n-doping at higher potential.
  • Base choices LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH) 2 , Ca(OH) 2 , Sr(OH) 2 , Ba(OH) 2 , ammonia (NH3 or NH4.0H), amines and its derivatives such as triethylamine, and nitrogen based organic base such as l,5-Diazabicyclo(4.3.0)non-5-ene (DBN), etc., both strong and weak bases.
  • NH3 or NH4.0H ammonia
  • amines and its derivatives such as triethylamine
  • nitrogen based organic base such as l,5-Diazabicyclo(4.3.0)non-5-ene (DBN), etc.
  • Acid choices H 2 SO4, H3PO4, HNO3, HC1, HBr, HI, HPFe, HTFSI, HFSI, HC1O4, HBrO 4 , HIO 4 , Acetic acid (HAC), citric acid (CeHsO?), H2SO3, HF, H2S, etc., both strong and week acids.
  • Polyvinyl alcohol partial elimination of H 2 O without decomposition lead to higher remaining weight. Weight remaining > 59.1%.
  • a base or acid can be added to the polyvinyl alcohol, such as, NaOH, or H2SO4 at 1% to 40% by weight ratio before heating process at Ar atmosphere.
  • the base or acid added PVA shows lower temperature H 2 O elimination and prevent from structure decomposition.
  • some remaining hydroxyl groups can also be oxidized to carbonyl groups to adjust the bandgap of the pi-pi conjugation to promote more n-doping at higher potential.
  • Fig. 8 Heating scan rate all at 0.2 °C/min, experiment done in Argon (Ar) atmosphere.
  • PVA Pure.
  • Fig. 12 TGA experiment done in Ar atmosphere of Pure PVA, and retrieve sample after heating to 240 0 C and cool down to ambient temperature.
  • Fig. 18 PVA:NaOH and Si electrode treated in Ar - SiPN240 cycling data.
  • Fig. 20 The electrode of SiPN240 can be lithiated to almost full capacity. This electrode is made with PVA:NaOH 10: 1 water solution with Si. (B) The electrode of SiP240
  • SUBSTITUTE SHEET (RULE 26) SUBSTITUTE SPECIFICATION - CLEAN COPY cannot be lithiated. This electrode is made with PVA 10% water solution with Si.
  • SUBSTITUTE SHEET (RULE 26) SUBSTITUTE SPECIFICATION - CLEAN COPY both of those included limits are also included in the invention.
  • the polymer formed has the following chemical structure: are independently any number from 5, 10, 50, 100, 500, 1000, 5000, 10000, 50000, 1000000, or any number with a range of any of two preceding numbers;
  • A is -OH, -OAc, F, Cl, Br, I, - -OCH3, -SO4R, -SO3R, -NH2, -NHR, -NR1R2, phenyl and/or phenyl derivatives; and
  • R, Ri, and/or R2 are each independently any organic groups.
  • the polymer of the present invention can be used as an electrode binder for Si, Sn,
  • SUBSTITUTE SHEET (RULE 26) SUBSTITUTE SPECIFICATION - CLEAN COPY and/or graphite based anode electrode for a lithium-ion or solid-state battery.
  • the present invention provides for an electrical or electronic device, such as a battery comprising the polymer of the present invention, or a electrode comprising the polymer of the present invention.
  • the polymer of the present invention can be built into pouch cells to test the performance of the polymers.
  • the polymer of the present invention can be used in both consumer electronic battery and electric vehicle battery. Unlike regular binder, which is not conductive, this polymer binder is both electrically and ionically conducting, as well as provide adhesion.
  • the present invention provides for a method of synthesizing the polymer of the present invention comprising step(s) described herein.
  • the electrodes and/or devices, or methods, of the present invention can further comprise element(s), component(s), or step(s) described in U.S. Provisional Patent Application Ser. No. 63/369,182, filed July 22, 2022, and PCT International Patent Application No. PCT/US2023/028482, filed July 24, 2023, both titled “Mixed solid-state ionic-electronic polymer conductors for electrochemical devices”, both of which are hereby incorporated by reference.
  • the present invention provides for a mixture comprising A and B, wherein A is a polyvinylalcohol (PVA), polyhydroxybutadiene ( OH ), polycyclodihydroxyhexene or polyhydroxybutadiene-cyclodihydroxyhexene ( OH ); and B is a base or acid.
  • A is a polyvinylalcohol (PVA), polyhydroxybutadiene ( OH ), polycyclodihydroxyhexene or polyhydroxybutadiene-cyclodihydroxyhexene ( OH ); and B is a base or acid.
  • the base is a compound listed in Table 1.
  • the base is a metal carbonate salt (such as, Na2COs or NaHCCh), a phosphate
  • SUBSTITUTE SHEET (RULE 26) SUBSTITUTE SPECIFICATION - CLEAN COPY salt (such as, NasPCk or Na2HPO4), or an organic base (such as Ammonia, Methylamine, Ethylamine, Diethylamine, Triethylamine, Hydroxylamine, Hydrazine, Aniline, Pyridine, and the like; or an organic superbase, such as a phosphazene, phosphane, amidine, and/or guanidines), or a mixture thereof.
  • an organic base such as Ammonia, Methylamine, Ethylamine, Diethylamine, Triethylamine, Hydroxylamine, Hydrazine, Aniline, Pyridine, and the like
  • an organic superbase such as a phosphazene, phosphane, amidine, and/or guanidines
  • the acid is a compound listed in Table 2.
  • B comprises from about 0.001% to about 99% by weight of the mixture.
  • the present invention provides for a method of making the mixture, comprising: (a) mixing A in water solution and B in water solution to form a mixture solution, and (b) optionally drying the mixture solution at an ambient or room temperature to separate water from the the mixture of A and B.
  • the method comprises one or more of the folowing steps: (1) Heating said mixture at the inert atmosphere to a range of about 50 - 800 °C at a time period of about 1 second to 48 hours, and cool down to ambient temperature to produce electrically conductive polymer.
  • the heating range can further narrow down to about 150 - 250 °C over a period of about 1 hour.
  • the heating range can further narrow down to about 150 - 250 °C over a period of about 1 hour.
  • the mixture solution is combined with lithium ion battery electrode materials, such as carbon, Si, SiOx, or Sn particles to make negative electrode.
  • A is used as electrode binder.
  • the electrode contains at least one carbon, Si, SiOx or Sn particle or a mixture of some.
  • Heating said electrode at the inert atmosphere to a range of about 50 - 800 °C at a time period of about 1 second to 48 hours, and cool down to ambient temperature to produce electrically conductive polymer binder in the electrode.
  • the heating range can further narrow down to about 150 - 250 °C over a period of about 1 hour.
  • Heating said electrode in at ambient air condition to a range of about 50 - 800 °C at a time period of about 1 second to 48 hours, and cool down to ambient temperature to produce electrically conductive polymer binder in the electrode.
  • the heating range can further narrow down to about 150 - 250 °C over a period of about 1 hour.
  • the heat-treated electrode is used to make a lithium-ion battery.
  • the starting materials are the commercial polybutadiene of molecular weight from 2 -butylene at 56 to 1,000,000,000,000 Dalton and could be infinitely high.
  • the brominating of the ally carbon position is done with a general processor, but keep the mole ratio of NBS and the polyb utadiene-mer (mer means a repeating unit in a polymer) in a range of 1 : 1 to 2: 1, with 1.1 : 1 as an particular embodiment.
  • NBS bromination at 25° were carried out in purified benzene using AIBN as initiator. All components of the reaction mixture were weighed, dissolved in benzene, and transferred quantitatively to the reaction flask. The reaction medium was degassed three times, sealed from the atmosphere by a stopcock, immersed in a water bath at 25°, and
  • SUBSTITUTE SHEET (RULE 26) SUBSTITUTE SPECIFICATION - CLEAN COPY magnetic stirring for 4 hr. The reaction solution was filtered and precipitated out in methanol and water, and dried at room temperature to yield brominated polybutadiene.
  • poly(l-bromobutadiene) was dissolved in DMF. 1 to 2 mole ratio of the NaHCCh to the poly(l-bromobutadiene)-mer was added to the DMF solution. While stirring, wl to 2 mole ratio of water was added dropwise to the stir solution at room temperature to 80 C. After reaction, the solution was filtered and product was precipitated out in hexane solvent. Water dialysis was performed on the product to rid of the salts in the polymer to yield the pure poly(l-hyroxylbutadiene).
  • poly(l-hyroxylbutadiene) and other related structures above can be used in fabrication of the electrochemical and other devices to provide both electron and ion dual charge conductivity.
  • Fig. 6 shows a scheme for converting polyvinyl alcohol into polyacetylene. It shows polyvinyl alcohol full elimination without decomposition. The weight loss is 40.9% of H2O, and weight remaining, 59.1% of polyacetylene. However, the loss of water is always happening with main chain decomposition during thermal treatment even in the inert atmosphere. In order to promote the formation of more polyacetylene structure, and less decomposition during heating process. A base or acid can be added to the polyvinyl alcohol, such as NaOH or H2SO4 before heating process. The base and acid added PVA shows lower onset temperature H2O elimination and prevents from structure decomposition.
  • Sample preparation is done in following two ways, as Method 1 and 2.
  • Method 1 Make 1% H2SO4 by weight water solution. Make 0.5%, 1% or 2% by
  • SUBSTITUTE SHEET (RULE 26) SUBSTITUTE SPECIFICATION - CLEAN COPY weight of NaOH water solution. Add 30 mL of the above solution to 1g of PVA and stirred overnight. Part of the polymer is dissolved and part are swelled in the water solution. The PVA polymer and acid or base solution is concentrated, and all the water is removed in a rotary evaporator at reduced pressure.
  • Fig. 8 shows PVA thermal decomposition during TGA process in Ar atmosphere.
  • PVA is a pure polymer sample of 130,000 Dalton molecular weight.
  • PVA with 1% weight of 30 mL NaOH solution, PVA:NaOH 10:3 by weight.
  • PVA with 1% weight of 30 mL H2SO4 solution, PVA:H 2 SO 4 10:3.
  • Fig. 7 shows partial elimination of water leaves some -OH functional groups in the structure. Partial elimination of hydroxide group of PVA leads to formation of polyacetylene conductive polymer with functional -OH groups in the polymer structure. These -OH groups can provide additional functions such as adhesion to a surface. The partial elimination can be controlled by thermal decomposition temperature and/or amount of acid or base added.
  • Fig. 9 shows an example of the PVA with 1% NaOH decomposition.
  • the first elimination temperature plateau is 200 °C to 300 °C wide range.
  • Fig. 13 is an example of the PVA with 0.5% NaOH solution processed sample, thermal scan at 6 °C/min heating, stopped at 240 °C TGA treatment in Ar atmosphere.
  • SUBSTITUTE SHEET (RULE 26) SUBSTITUTE SPECIFICATION - CLEAN COPY sample weight is very close to the theoretical polyacetylene weight based on Scheme 3. The sample collected sample is red colored.
  • Method 2 PVA of 5g is mixed with 45g of water and reflux at 100 °C for 1 hour to completely dissolve the PVA in water to form a clear solution.
  • concentration of the PVA water solution is 10% by weight.
  • 5% weight of PVA water solution also made in the similar way.
  • 1 g of NaOH is dissolved in 9g of water to make a 10% NaOH solution.
  • 0.69g of LiOH is dissolved in 13.29 g of water to make a 5% of LiOH solution.
  • PVA:NaOH 100:1 by weight was made with mixing 60g of 5% PVA solution and 300 mg of 10% NaOH solution.
  • PVA:NaOH 100:2 by weight was made with mixing 20g of 5% PVA solution and 200 mg of 10% NaOH solution.
  • PVA:NaOH 10: 1 by weight was made with mixing 10g of 10% PVA solution and 1g of 10% NaOH solution.
  • PVA:NaOH 10:5 by weight was made with mixing 10g of PVA 10% solution and 5g of 10% NaOH solution.
  • PVA: LiOH 10:0.5 by weight was made mixing with 10g of 10% PVA solution and 1g of 5% LiOH solution.
  • PAV:LiOH 10:2 by weight was made with mixing 10g of 10% PVA solution and 4g of 5% LiOH solution.
  • Sample synthesized include PVA 10% solution, no other dopant.
  • PVA and NaOH or LiOH solutions for making polymer film or electrode slurry.
  • 3-5 drops of above polymer and NaOH solutions sample is spread out to a ⁇ 2cm by 2cm cover glass.
  • a pure PVA 10% solution is also applied to a cover glass as a control.
  • Three similar samples of each solution were made. All the samples are heated treated dried and process in a tube furnace under flow Ar gas following the heating procedure:
  • PVA solution, PVA and LiOH or NaOH solution of different compositions spread on cover glass ready for thermal treatment in tube furnace. Purge for 2.5hrs with Ar gas.
  • a multimeter is used to measure the lateral/in-plane resistivity/conductivity of the polymer film.
  • the two electrode pins are about 1-2 mm apart on the surface of the polymer film to measure the PAV: LiOH resistivity of the film. Immediate after the films take out of the inert gas tube furnace, none of the samples show measurable film lateral electrical conductivity using the multimeter. The multimeter reading of an infinity resistivity of the lateral film resistivity of all samples.
  • the polymer films of PVA:NaOH 10: 1 and PVA:NaOH 10:5 showed a resistivity reading of 1-50 Mohm of lateral resistivity, corresponding to a significant conductivity of the polymer film after the film expose to ambient air for 15 minutes.
  • the pure PVA sample showed infinity resistivity and no conductivity after exposure to air as well as exposure to I2 vapor.
  • Polymer film of PVA:NaOH 10: 1 on cover glass have been synthesized after the thermal treatment and expose to air for 15 minutes show latera conductivity.
  • the PVA polymer and NaOH solution samples synthesized include: PVA:NaOH 100:2 and PVA:NaOH 10: 1.
  • Heating starts at 25 °C to 240 °C at liner temperature increase in 3 hrs. Hold at 240 °C for 10 minutes, and cool down to room temperature at ambient temperature.
  • the polymer films show infinite resistivity based on the lateral multimeter measurement. However, when the 10: 1 sample treated in I2 for 15 minutes, and the 100:2 sample treated overnight, the film shows 1-50 Mohm resistivity.
  • PVA:NaOH 10:1 by weight was made with mixing 10g of 10% PVA solution and 1g of 10% NaOH solution. This composition is used to make 2:8 ratio of PVA and Si electrode slurry, containing NaOH. 1 g of Si micronsize particle (1-5 pm diameter) is mixed with 2.75 g of the PVA:NaOH 10: 1 mixture in a small agate mortar, and mixed with a agate pestle for 10 minutes to form a homogenous slurry.
  • the slurry was coated on a thin Cu sheet using a doctor blade with a 50 pm gap at a 2 meter/min rate.
  • the electrode was dried in air for ⁇ 1 hour.
  • the PVA and Si electrode slurry is coated onto an electrode laminate on a Cu current collector.
  • One piece of the electrode is dried at 80 °C under vacuum overnight. This electrode is named SiPN80.
  • the Si loading of the electrode is 1.1 mg/cm 2 .
  • the other piece of the electrode was processed in a tube furnace follow the procedure. The it is purged for 2.5hrs with Ar gas. Heating started at 25 °C to 240 °C with liner temperature increase in 3 hrs. Hold at 240 °C for 10 minutes, and cooled down to room temperature at ambient temperature.
  • This electrode is named SiPN240.
  • the Si loading of the electrode is 1.1 mg/cm 2 .
  • the other piece of the electrode was processed in a tube furnace follow the procedure. Heating start at 25 °C to 240 °C with liner temperature increase in 3 hrs in air. Hold at 240 °C for 10 minutes, and cool down to room temperature at ambient temperature.
  • This electrode is named SiPNA240.
  • the other piece of the electrode was processed in a tube furnace follow the procedure. Heating start at 25 °C to 150 °C with liner temperature increase in 1 hr in air. Hold at 240 °C for 10 minutes, and cool down to room temperature at ambient temperature.
  • This electrode is named SiPNA150.
  • PVA and Si electrode with or without NaOH doping are thermal treat in a tube furnace.
  • the PVA was synthesized using a 10% water solution. This composition is used to make 2:8 ratio of PVA and Si electrode slurry. 1 g of Si micron-sized particle (1-5 pm diameter) is mixed with 2.0 g of the PVA 10% water solution in a small agate mortar, and mixed with an agate pestle for 10 minutes to form a homogenous slurry.
  • the slurry was coated on a thin Cu sheet using a doctor blade with a 50 pm gap at a 2 meter/min rate.
  • the electrode was dried in air for ⁇ 1 hour.
  • One piece of the electrode is dried at 80 °C under vacuum overnight. This electrode is named SiP80.
  • Another piece of the electrode was processed in a tube furnace follow the procedure. Purge for 2.5hrs with Ar gas. Heating start at 25 °C to 240 °C with liner temperature increase in 3 hrs. Hold at 240 °C for 10 minutes, and cool down to room temperature at ambient temperature. This electrode is named SiP240.
  • PVA:NaOH 100:2 by weight was made with mixing 10g of 5% PVA solution and 0.1 g of 10% NaOH solution. This composition is used to make 2:8 ratio of PVA and Si electrode slurry, containing NaOH. 1 g of Si micronsize particle (1-5 pm diameter) is mixed with 5.10 g of the PVA:NaOH 100:2 mixture in a small agate mortar, and mixed with an agate pestle for 10 minutes to form a homogenous slurry.
  • the Si electrode was made with a PVA:NaOH 100:2 mixture.
  • the poly(l-hyroxylbutadiene) and PVA (Scheme 1,2,3) with NaOH can be used as electrode binders for carbon, Si, Sn and other alloy based composite electrodes.
  • This class of functional conductive polymer materials provides strong adhesion to the Si, Sn and carbon materials and Cu current collectors as an effective electrode binder.
  • Thermal treatment of the polymer materials leads to all or partial loss of the hydroxyl groups to provide permanent and superb pathways ranging from Angstroms to Nanometers in the polymer films for lithium ion transport.
  • the polymers When the polymers are applied on surface of Si or graphite, the polymers in touch with the active materials (Si, Sn and Carbon) surface transforms into passivation layer during the electrochemical process to provide very strong passivation to the active materials surface.
  • the ion pathway in the polymer binder due to the thermal decomposition of hydroxyl groups provides ion transport.
  • this functional binder Unlike the usage of only a few percent of conventional binders, it is preferentially to use this functional binder to cover the entire active materials particles surface to provide both strong adhesion and surface protection.
  • this class of electrode binders works for the anode for Na and K based battery, and for solid-state batteries.
  • Coin cells (2032, Hohsen Co.) were assembled in an argon-filled glovebox. A 14.42 mm diameter disk was punched out as a working electrode. Lithium chip (16.0 mm in diameter, MTI Co.), is used as the counter electrodes in half. 60 pL of lithium-ion electrolyte of IM LiPFe in EC EMC (3:7 by weight) and fluoroethylene carbonate (FEC, typically 5 wt.%) is used for coin cell testing. The Si loading of the electrode is ⁇ 1.0 mg/cm 2 . Celgard 2400 separator (1.7 cm in diameter) was placed between the working electrode and the counter electrode.
  • the galvanostatic cycling performance of the assembled coin cells was evaluated with Maccor Cycler in a thermal chamber at 30 °C.
  • the C-rate was determined based on the theoretical capacity upon a full lithiation of Si materials of 4200 mAh/g.
  • the Cell is rested for 4 hours and lithiated at C/25 current rate.
  • Fig. 20. The electrode of SiPN240 can be lithiated to almost full capacity. This
  • SUBSTITUTE SHEET (RULE 26) SUBSTITUTE SPECIFICATION - CLEAN COPY electrode is made with PVA:NaOH 10: 1 water solution with Si. (B) The electrode of SiP240 cannot be lithiated. This electrode is made with PVA 10% water solution with Si.
  • PVA NaOH films are made from solution on cover glass.
  • the PVA:NaOH films undergo heat treatment in a tube furnace of under Ar.
  • PVA:NaOH and PVA:LiOH combinations are synthesized under water solutions.
  • the PVA:NaOH and PVA:LiOH solution are cast droplet on cover glass, which then undergo heat treatment on the cover glass under Ar.
  • the PVA:NaOH casted films after heat treatment showed lateral electrical conductivity.
  • PVA:NaOH and Si particles are used to make an electrode slurry.
  • the PVA:NaOH and Si are cast to make a PVA:NaOH and Si electrode.
  • the PVA:NaOH and Si electrode is air dried.
  • the PVA:NaOH and Si electrode can be cut.
  • the PVA:NaOH and Si electrode can undergo heat treatment, such as in a tube furnace.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un polymère capable de conductance. Dans certains modes de réalisation, le polymère est utile dans la fabrication d'un dispositif électrique ou électronique, tel qu'une batterie.
PCT/US2024/015840 2023-02-14 2024-02-14 Conducteur de charge polymère Ceased WO2024173584A2 (fr)

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Publication number Priority date Publication date Assignee Title
EP1090956A1 (fr) * 1999-03-23 2001-04-11 Nisshinbo Industries, Inc. Composition pour polymere solide a conductivite ionique, polyelectrolyte solide a conductivite ionique, resine de liaison et batterie secondaire
US8945429B2 (en) * 2012-04-11 2015-02-03 Energy Materials Corporation Electrically conducting thin films and methods of making same

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