WO2024059937A1

WO2024059937A1 - Metallated catechol derivatives useful for lithium battery electrodes

Info

Publication number: WO2024059937A1
Application number: PCT/CA2023/051242
Authority: WO
Inventors: Dwight Seferos; Tyler SCHON; Grayson INGRAM; Bryony MCALLISTER; Soyoung An
Original assignee: University of Toronto
Current assignee: University of Toronto
Priority date: 2022-09-22
Filing date: 2023-09-19
Publication date: 2024-03-28
Anticipated expiration: 2025-03-22

Abstract

The present disclosure relates to an electroactive material for use as a secondary battery electrode material and a secondary battery device including the same. Particularly, the present disclosure relates to the use of pre-metallated catechol derivatives of the following formula [PCAT], wherein Ar is an aromatic group containing two or more ortho-positioned alkali oxide redox group, X is a methylene group, an oxygen atom, an imine group both small molecule and main chain polymers, M is a counter-ion chosen from lithium, sodium, potassium, magnesium, or calcium, as the basis of an electroactive material for metal-ion batteries.

Description

METALLATED CATECHOL DERIVATIVES USEFUL FOR LITHIUM BATTERY ELECTRODES

FIELD

The present disclosure relates to electroactive materials that are useful for a secondary battery electrode material and the secondary battery device including the same. Particularly, the present disclosure relates to the use of premetallated catechol derivatives, both small molecule and main chain polymers, as the basis of an electroactive material for metal-ion batteries.

BACKGROUND

Sustainable, high capacity, and low cost materials for energy storage devices, including lithium ion batteries, sodium ion batteries, and magnesium ion batteries, are urgently needed due to the increasing use of batteries for consumer electronics, new portable electronics, electric vehicles and grid-level energy storage. Current lithium ion batteries use transition metal, in particular cobalt-containing, cathodes to store energy. These metal electrodes require mining, extraction, and other energy intensive processes to form battery-grade materials which are an environmental burden due to the release of substantial amounts of greenhouse gases and toxic waste by-products generated in these steps.

Additionally, the supply chain of cobalt, arguably the most important lithium ion battery element, is unstable and it is expected that the cost of cobalt will increase substantially in the next few years, causing an economic crisis for the deployment and storage of renewable energy sources, electric vehicles, and portable electronics unless a suitable alternative to cobalt-containing cathodes is found. Also, due to the high theoretical gravimetric capacity of organic materials, they open up the opportunity to make batteries lightweight, with modelled cell-level specific energies up to 800 Wh/kg. This can enable the next generation of electric aviation, drone technology, battery-operated marine applications, and even electric vehicle use. An organic material that can be used to replace metal-containing electrodes in lithium ion batteries is very desirable.

SUMMARY

Organic carbonyl compounds are popular choices for battery cathode materials due to their high reversibility, high capacity (>200 mAh/g), and abundance. Materials of this kind have been thoroughly demonstrated as lithium ion battery cathode materials in both the academic and patent literature. However, there has been major issues with previous disclosures that have impeded their commercialization. First of all, for high energy battery materials, the bulk density of the materials has a significant effect on the system levels performance in a full cell and recent studies by the inventors have determined that a materials level capacity of at least 300 mAh/g and a voltage of >2.8 V vs Li/Li⁺ is required to compete in any market. Additionally, the protic nature of most reported materials precludes their use in standard lithium ion batteries because in operation of a standard lithium ion battery, the protons will be stripped from the material upon oxidation which can increase the acidity of the electrolyte. This in turn could corrode various internal components of the battery cell and also generate hydrogen gas when the protons come in contact with the low potential anode, both of which cause serious safety issues. Lastly, organic electrodes still suffer from poor cycling stability due to dissolution in the electrolyte.

The present disclosure provides the use of polymeric and small molecule catechol derivatives that are pre-metallated prior to constructing a battery test cell and use in a liquid or solid state cell. The use of a catechol derivative raises the voltage to above 2.8 V vs Li/Li⁺ due to the coordination of lithium ions to the ortho-hydroquinone groups that lowers the lowest unoccupied molecule orbital. Also, pre-metallated the compounds removes acidic protons that can cause safety issues for lithium ion battery operation. Also, by forming a main chain polymer with the catechol derivatives the solubility of the material which increases cycling stability. As an alternative, we disclose that the use of premetallated small molecules paired with a solid electrolyte provides an increased cycling stability due to the inability to dissolve, or the retardation of the rate of dissolution of, the small molecule to dissolve in the solid. The materials are based on organic materials that contain C, H, O, N, and/or Li atoms. The electroactive functionality is related to the carbonyl groups that are located on the aromatic ring.

The present disclosure provides a catechol derivative that comprised of an aromatic ring or a series of fused and/or chemically bonded aromatic rings that contain electrochemically active ortho-positioned hydroxyl groups that have been treated with a metal base to replace the acidic protons with a metal ion. Thus, the present disclosure provides an electroactive material, comprising the molecular structures PCAT:

[PCAT]:

in which Ar is an aromatic group containing two or more ortho-positioned alkali oxide redox groups,

X is a methylene group, an oxygen atom, an imine group substituted with a hydrogen atom, a methyl group, or an alkali metal ion;

H is hydrogen; O is oxygen

M is a counter-ion chosen from lithium, sodium, potassium, magnesium, or calcium; n is the number of alkali/hydroxy oxide units ranging from 2 to 4; k is the number of repeating units ranging from 0 to 3; and m is the number of repeating units ranging from 1 to 2,000,000.

The molecular structures PCAT may be produced using precursors selected from the following structures:

where n is an integer in a range from 2 to about 100.

The aromatic group may be any one of the following base structures:

ucture may be PCAT1 :

in which X is any one of a methylene group, an oxygen atom, an imine group substituted with a hydrogen atom, a methyl group, or an alkali metal ion; and

M is a counter-ion comprised of lithium, sodium, potassium, magnesium, or calcium. In this aspect, M may be lithium, n is 2, k is 0 and m is 1 .

Alternatively, k is 1 and X is a methylene group and m is between 1 and 1000.

The electroactive material may comprise the molecular structure PCAT2:

[PCAT2]:

where X is a methylene group, an oxygen atom, an imine group substituted with a hydrogen atom, a methyl group, or an alkali metal ion;

M is a counter-ion chosen from lithium, sodium, potassium, magnesium, or calcium; H is hydrogen;

O is oxygen; n is the number of alkali/hydroxy oxide units ranging from 2 to 4; k is the number of repeating units ranging from 0 to 3; and m is the number of repeating units ranging from 1 to 2,000,000.

In this embodiment M may be lithium, n may be 2, k may be 0 and m may be 1.

Alternatively, k may be 1 and X is a methylene group and m may be between 1 and 1000.

The present disclosure provides a method of making a subset of PCAT using METHOD 1 :

[METHOD 1]:

wherein M is a counter-ion chosen from lithium, sodium, potassium, magnesium, or calcium;

Ar is an aromatic group contains two or more ortho-positioned alkali oxide redox groups. n is the number of alkali metal oxide units ranging from 2 to 4; k is the number of repeating units ranging from 0 to 3; m is the number of repeating units ranging from 1 to 2,000,000.

R1 is a reagent chosen from formaldehyde or paraformaldehyde;

B1 is a base used to catalyze the condensation reaction and replace the acidic protons with a counter-ion that is any one or combination of lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, lithium hydride, sodium hydride, potassium hydride, magnesium hydride, and calcium hydride; S1 is a solvent that solubilizes the reagents that can be chosen from any one or combination of water, methanol, ethanol, propanol, N-methyl pyrollidone, toluene, tetrahydrofuran, dimethylsulfoxide and dimethyl formamide;

T1 is a temperature between about -20 and about 250 degrees Celsius; and

P1 is a pressure between about 0.5 and about 20 atmospheres.

The aromatic group may be any one of the following base structures:

The present disclosure further provides a method to make a precursor of a subset of PCAT is synthesized by Method 2:

[METHOD 2]:

wherein X is an oxygen atom, an imine group substituted with a hydrogen atom, a methyl group, or an alkali metal ion;

Ar is an aromatic group that contains two or more ortho-positioned akali oxide redox groups.

M is a counter-ion chosen from lithium, sodium, potassium, magnesium, or calcium; n is the number of hydroxy oxide units ranging from 2 to 4; k is the number of repeating units ranging from 0 to 3; m is the number of repeating units ranging from 1 to 2,000,000.

0x1 is an oxidant used to oxidatively polymerize the catechol derivative and is chosen from any one or combination of iron (III) chloride, ammonium persulfate and an electrochemical oxidation process;

S1 is a solvent that solubilizes the reagents that is any one or combination of water, methanol, ethanol, propanol, N-methyl pyrollidone, toluene, tetrahydrofuran, dimethylsulfoxide, and dimethyl formamide;

T1 is a temperature between about -20 and about 250 degrees Celsius;

P1 is a pressure between about 0.5 and about 20 atmospheres; Red1 is a reductant used to reduce the compounds to the hydroquinone form after oxidative polymerization and is chosen from any one or combination of sodium borohydride, sodium thiosulphate, hydrogen and lithium borohydride.

The aromatic group may be any one of the following base structures:

The present disclosure also provides a method to synthesize PCAT by

Method 3:

[METHOD 3]:

Ar is an aromatic group contains two or more ortho-positioned alkali oxide redox groups; wherein M is a counter-ion chosen from lithium, sodium, potassium, magnesium, or calcium; n is the number of alkali/hydroxy oxide units ranging from 2 to 4; k is the number of repeating units ranging from 0 to 3; m is the number of repeating units ranging from 1 to 2,000,000.

B1 is a base used to catalyze the condensation reaction and replace the acidic protons with a counter-ion that is any one or combination of lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, lithium hydride, sodium hydride, potassium hydride, magnesium hydride and calcium hydride;

S1 is a solvent that solubilizes the reagents that is any one or combination of water, methanol, ethanol, propanol, N-methyl pyrollidone, toluene, tetrahydrofuran, dimethylsulfoxide, and dimethyl formamide; T1 is a temperature between about -20 and about 250 degrees Celsius; and

P1 is a pressure between about 0.5 and about 20 atmospheres.

The aromatic group may be any one of the following base structures:

These electroactive materials may be incorporated into an energy storage device. The energy storage device may be any of, but not limited to, a lithium ion battery, sodium ion battery, magnesium ion battery, aluminium ion battery, potassium ion battery, a calcium battery, or a hybrid device. In some embodiments the energy storage device may be a battery including an electrolyte, and the electrolyte comprises a salt dissolved in an organic electrolyte.

In some embodiments the energy storage device may be a battery including an electrolyte, and the electrolyte comprises a salt dissolved in a gel polymer electrolyte with an organic solvent.

In some embodiments the energy storage device may be a battery including an electrolyte, and the electrolyte comprises a solid electrolyte.

The energy storage devices may be constructed with flexible mechanical properties and a/or flexible form factor.

A further understanding of the functional and advantageous aspects of the present disclosure can be realized by reference to the following detailed description and drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 Proton nuclear magnetic resonance spectra of formula PCAT1 wherein k is 0, M is lithium, n is 2, and m is 1 in D2O.

FIG. 2 Lithium nuclear magnetic resonance spectra of formula PCAT1 wherein k is 0, M is lithium, n is 2, and m is 1 in D2O

FIG. 3 Fourier transform infrared spectra of formula PCAT1 wherein k is 0, M is lithium, n is 2, and m is 1 .

FIG. 4A shows galvanostatic charge/discharge curves (max 400 mAh/g) of a test coin cell with a cathode comprised of formula PCAT1 wherein k is 0, M is lithium, n is 2, and m is 1 . FIG. 4B shows galvanostatic charge/discharge curves (max 50 mAh/g) of a test coin cell with a cathode comprised of formula PCAT1 wherein k is 0, M is lithium, n is 2, and m is 1 .

FIG. 5 Fourier transform infrared spectra of formula PCAT1 wherein X is a methylene group, k is 1 , M is lithium, n is 2, and m is an integer between 2 and 2,000,000.

FIG. 6 Galvanostatic charge/discharge curves of a test coin cell with a cathode comprised of formula PCAT1 wherein X is a methylene group, k is 1 , M is lithium, n is 2, and m is an integer between 2 and 2,000,000.

DETAILED DESCRIPTION

Without limitation, the systems described herein are directed towards chemical compounds and their use in energy storage devices. A common theme of these materials is their lack of acidic protons which can cause issues upon cycling. Additionally, the use of these materials in solid state cells with can yield battery performance that is much higher than their liquid cell counterparts. As required, embodiments of the present disclosure are disclosed herein. However, the disclosed embodiments are merely exemplary, and it should be understood that the embodiments of the present disclosure may be embodied in many various and alternative forms.

The figures are not to scale and some features may be exaggerated or minimized to show details of particular elements while related elements may have been eliminated to prevent obscuring novel aspects. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present disclosure. For purposes of teaching and not limitation, the illustrated embodiments are directed compounds, their method of synthesis, and electrode materials produced from these compounds for use in energy storage devices.

As used herein, the term “about”, when used in conjunction with ranges of dimensions, velocities, temperatures or other physical properties or characteristics is meant to cover slight variations that may exist in the upper and lower limits of the ranges of dimensions as to not exclude embodiments where on average most of the dimensions are satisfied but where statistically dimensions may exist outside this region.

Broadly speaking, the present disclosure provides compounds comprising an aromatic ring with at least 2 alkali oxide groups in an ortho position relative to each other in a small molecule or main chain polymeric form. This compound can be made through a variety of synthetic routes that are standard in organic and polymeric chemistry. The advantages of these compounds are their ease of synthesis, derivation from highly available feedstocks, their high energy compared to other organic compounds that can function as a metal-ion battery cathodes, their high electrochemical activity, their adhesion to themselves and different substrates, their lack of acidic protons that can cause safety issues in operation, and their mechanical properties that include flexibility. Due to the ability of these materials to reversibly accept charges over a specific voltage range defined by their lowest unoccupied molecular orbitals, they are well suited for energy storage applications.

The present disclosure provides an electroactive material that has a molecular structure according to formula PCAT:

Ar is an aromatic group contains two or more ortho-positioned akali oxide redox groups. The aromatic groups can be chosen from the following base structures:

M is a counter-ion chosen from lithium, sodium, potassium, magnesium, or calcium; n is the number of alkali metal oxide units ranging from 2 to 4; k is the number of repeating units ranging from 0 to 3; m is the number of repeating units ranging from 1 to 2,000,000.

The present disclosure describes a method to synthesize a subset of PCAT using Method 1 :

[METHOD 1]:

n is the number of alkali metal oxide units ranging from 2 to 4; k is the number of repeating units ranging from 0 to 3; m is the number of repeating units ranging from 1 to 2,000,000.

R1 is a reagent chosen from formaldehyde or paraformaldehyde;

B1 is a base used to catalyze the condensation reaction and replace the acidic protons with a counter-ion that can be any one of combination of lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, lithium hydride, sodium hydride, potassium hydride, magnesium hydride, or calcium hydride;

S1 is a solvent that solubilizes the reagents that can be chosen from any one or combination of water, methanol, ethanol, propanol, N-methyl pyrollidone, toluene, tetrahydrofuran, dimethylsulfoxide, or dimethyl formamide;

T1 is a temperature between -20 and 250 degrees Celsius;

P1 is a pressure between 0.5 and 20 atmospheres.

A precursor of a subset of PCAT can also be synthesized by Method 2: [METHOD 2]:

0x1 is an oxidant used to oxidatively polymerize the catechol derivative and is chosen from one or a combination of iron (III) chloride, ammonium persulfate, and an electrochemical oxidation; S1 is a solvent that solubilizes the reagents that can be chosen from any one or combination of water, methanol, ethanol, propanol, N-methyl pyrollidone, toluene, tetrahydrofuran, dimethylsulfoxide, or dimethyl formamide;

T1 is a temperature between -20 and 250 degrees Celsius; P1 is a pressure between 0.5 and 20 atmospheres;

Red1 is a reductant used to reduce the compounds to the hydroquinone form after oxidative polymerization and is chosen from one or a combination of sodium borohydride, sodium thiosulphate, hydrogen, or lithium borohydride.

The present disclosure also reports a method to synthesize PCAT by Method 3:

[METHOD 3]:

Wherein M is a counter-ion chosen from lithium, sodium, potassium, magnesium, or calcium; n is the number of alkali/hydroxy oxide units ranging from 2 to 4; k is the number of repeating units ranging from 0 to 3; m is the number of repeating units ranging from 1 to 2,000,000.

B1 is a base used to catalyze the condensation reaction and replace the acidic protons with a counter-ion that can be any one of combination of lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, lithium hydride, sodium hydride, potassium hydride, magnesium hydride, or calcium hydride; S1 is a solvent that solubilizes the reagents that can be chosen from any one or combination of water, methanol, ethanol, propanol, N-methyl pyrollidone, toluene, tetrahydrofuran, dimethylsulfoxide, or dimethyl formamide;

T1 is a temperature between -20 and 250 degrees Celsius;

P1 is a pressure between 0.5 and 20 atmospheres.

The present disclosure relates to a subset of PCAT as an electroactive material in an energy storage device having a molecular structure according to formula PCAT1 given here below:

[PCAT1]:

Wherein X is a methylene group, an oxygen atom, an imine group substituted with a hydrogen atom, a methyl group, or an alkali metal ion;

M is a counter-ion chosen from lithium, sodium, potassium, magnesium, or calcium; n is the number of alkali oxide units ranging from 2 to 4; k is the number of repeating units ranging from 0 to 3; m is the number of repeating units ranging from 1 to 2,000,000.

The present disclosure describes a method to synthesize a subset of

PCAT1 using Method 1 :

[METHOD 1]:

R1 is a reagent chosen from formaldehyde or paraformaldehyde;

T1 is a temperature between -20 and 250 degrees Celsius;

P1 is a pressure between 0.5 and 20 atmospheres.

Especially the following procedure:

80 °C, 18 hrs, Ar

The molecular structure PCAT structures may be produced using precursors including:

where n is an integer in a range from 2 to about 100. A precursor of a subset of PCAT1 can also be synthesized by Method 2:

[METHOD 2]:

0x1 is an oxidant used to oxidatively polymerize the catechol derivative and is chosen from one or a combination of iron (III) chloride, ammonium persulfate, and an electrochemical oxidation;

T1 is a temperature between -20 and 250 degrees Celsius;

P1 is a pressure between 0.5 and 20 atmospheres;

Red1 is a reductant used to reduce the compounds to the hydroquinone form after oxidative polymerization and is chosen from one or a combination of sodium borohydride, sodium thiosulphate, hydrogen, or lithium borohydride. The present disclosure also reports a method to synthesize PCAT1 by

Method 3:

[METHOD 3]:

wherein X is an oxygen atom, an imine group substituted with a hydrogen atom, a methyl group, or an alkali metal ion; wherein M is a counter-ion chosen from lithium, sodium, potassium, magnesium, or calcium; n is the number of alkali/hydroxy oxide units ranging from 2 to 4; k is the number of repeating units ranging from 0 to 3; m is the number of repeating units ranging from 1 to 2,000,000.

T1 is a temperature between -20 and 250 degrees Celsius;

P1 is a pressure between 0.5 and 20 atmospheres. The present disclosure also relates to a subset of PCAT as an electroactive material in an energy storage device having a molecular structure according to formula PCAT2 given here below:

[PCAT2]:

The present disclosure also relates to a subset of PCAT as an electroactive material in an energy storage device having a molecular structure according to formula PCAT3 given here below:

[PCAT3]:

wherein X is, independently, a methylene group, an oxygen atom, an imine group substituted with a hydrogen atom, a methyl group, or an alkali metal ion;

The present disclosure also relates to a subset of PCAT as an electroactive material in an energy storage device having a molecular structure according to formula PCAT4 given here below:

[PCAT4]:

The present disclosure also relates to a subset of PCAT as an electroactive material in an energy storage device having a molecular structure according to formula PCAT5 given here below:

[PCAT5]:

M is a counter-ion chosen from lithium, sodium, potassium, magnesium, or calcium; n is the number of alkali metal oxide units ranging from 2 to 4; k is the number of repeating units ranging from 0 to 3; m is the number of repeating units ranging from 1 to 2,000,000. EXAMPLE 1

For a test example, we describe the synthesis, characterization, and performance of a lithium battery with an electrode material described by

PCAT1 : [PCAT1]:

In this test example of PCAT1 , k is 0, M is lithium, n is 2, and m is 1 .

Hereafter, this specific example is referred to as compound A.

Following the scheme described in Method 6, the material was lithiated with a lithium base, where the acidic protons were replaced with lithium counter ions (FIG. 2):

[Method 6]:

wherein k is 0, M is lithium, n is 2, m is 1 , B1 is lithium hydroxide, S1 is anhydrous methanol, T1 is 25 degrees Celsius, and P1 is 1 atmosphere.

Synthesis of Compound A

According to Method 6 described above, 10 g of catechol was dissolved in 400 mL of anhydrous methanol in a flame dried round bottom flask that was kept under argon. After dissolution of catechol, the solution was cooled in an ice bath and 4.36 g of lithium hydroxide was added. The mixture was allowed to warm to room temperature and it was stirred for 20 hours. After the reaction was complete, the methanol was removed by a rotary evaporator and the compound was dried under vacuum for 3 days. The compound was produced in quantitative yield.

Characterization of Compound A

The resultant Compound A was characterized by a variety of techniques standard in organic small molecule characterization. From proton nuclear magnetic resonance spectroscopy (see FIG. 1) in D2O, two multiplet peaks, that integrate to the same values, situated between 6.85 and 7.0 ppm are significantly shifted downfield compared to the starting material by approximately 0.2 ppm which indicated that the aromatic ring is more electron rich, which is to be expected for a deprotonated phenol species. The compound was also characterized by lithium proton nuclear magnetic resonance spectroscopy (see FIG. 2) in D2O that showed a single peak at 0.17 ppm which is similar to that of free lithium salts showing that lithium ions likely dissociate from Compound A in an aqueous solution at neutral pH.

The compound was also characterized with fourier transform infrared spectroscopy (FIG. 3) which shows the absence of a hydroxyl stretch above 3000 cm'¹ and peaks that are similar to the starting material catechol including a stretch at -1504 cm^-1 which can be attributed to the aromatic C=C bonds within Compound A. Electrode Characterization

To test the applicability of Compound A for a lithium battery cathode, electrodes were cast of the material in a composite of carbon Super P to provide an electrically conductive network within the electrode, an ionically conductive polymer polypropylene carbonate) (molecular weight ~ 50kDa) to bind the materials together and enhance ionic conductivity, and a lithium bis(trifluoromethanesulfonyl)imide salt to provide free lithium ions in the electrolyte in a ratio of 125:75:40:10, respectively, with 1.7 mL of acetonitrile as the dispersing and casting solvent.

Lithium ion battery testing and characterization

To test the electrodes, test coin cells were constructed using lithium metal as the counter electrode and a solvent of 1 M lithium bis(trifluoromethanesulfonyl)imide in tetraethylene glycol dimethyl ether. To determine the capacity and coulombic efficiency of the material, galvanostatic charge/discharge experiments were run at a current of 50 mA/g (see FIG. 4A) of active material in a voltage window of 2V to 4V. In the first charge, the electrode exhibited a capacity of 389 mAh/g (see FIG. 4B) and a discharge capacity of 32 mAh/g at a coulombic efficiency of 8.2% and the charge and discharge capacity of the third cycle were 33 mAh/g and 25 mAh/g respectively. This suggests that the compound dissolves in the electrolyte when charged and diminishes the capacity substantially. This is supported by the low coulombic efficiency in the first cycle, where the majority of the compound is dissolved into the electrolyte when charged and results in the active material’s discharge becoming inaccessible. EXAMPLE 2

For a second test example, we describe the synthesis, characterization, and performance of a lithium battery (performance shown in FIG. 6) with an electrode material described by PCAT1 :

In this test example of PCAT1 , X is a methylene group, k is 1 , M is lithium, n is 2, and m is an integer between 2 and 2,000,000. Hereafter, this specific example is referred to as Compound B.

Following the scheme described in Method 4, the material was synthesized by a base-catalyzed condensation reaction:

[Method 4]:

wherein X is a methylene group, k is 1 , M is lithium, n is 2, m is an integer between 2 and 2,000,000, B1 is lithium hydroxide, R1 is paraformaldehyde, S1 is anhydrous methanol, T1 is 80 degrees Celsius, and P1 is 1 atmosphere. Synthesis of Compound B

According to Method 4 described above, 5 g of catechol was dissolved in 100 mL of argon-sparged methanol in a 3-necked flask under argon gas. 2.18g of lithium hydroxide and 1.36g of paraformaldehyde were dissolved in a separate flask containing 60 mL of anhydrous methanol under argon. The lithium hydroxide and paraformaldehyde solution were then added to the catechol solution by syringe at a rate of 2mL/minute. The reaction mixture was then heated at 80 degrees Celsius for 18 hours, cooled, and the solids were then filtered.

Characterization of Compound A

Due to the insoluble nature of Compound B, it could only be characterized by fourier transform infrared spectroscopy (see FIG. 5) which shows a small peak in the 3000 to 3750 cm^-1 which indicates that the compound either has residual methanol trapped within the polymeric structure or it has residual moisture trapped within the polymeric structure from the atmosphere. The region below 1500 cm^-1 is quite broad due to the lack of regioselectivity of the reaction and the possibility of crosslinking which creates a distribution of bond stretching frequencies but, notably, has a peak at 1428 cm'¹ which can be attributed to the C=C bonds within the aromatic ring suggesting that the aromatic ring is still intact.

Electrode Characterization

To test the applicability of Compound B for a lithium battery cathode, electrodes were cast of the material in a composite of carbon Super P to provide an electrically conductive network within the electrode, and poly(vinylidene fluoride) to bind the materials together in a ratio of 55:25:20, respectively, with 1.145 mL of N-methyl pyrrolidone as the dispersing and casting solvent.

Lithium ion battery testing and characterization

To test the electrodes, test coin cells were constructed using lithium metal as the counter electrode and a solvent of 1 M lithium hexafluorophosphate in ethylene carbonate, dimethyl carbonate, and diethyl carbonate in a weight ratio of 4:3:3. To determine the capacity and coulombic efficiency of the material, galvanostatic charge/discharge experiments were run at a current of 5 mA/g of active material in a voltage window of 2V to 4V. In the first charge, the electrode exhibited a capacity of 76 mAh/g and a discharge capacity of 30 mAh/g at a coulombic efficiency of 39% and the charge and discharge capacity of the third cycle were 13 mAh/g and 10 mAh/g respectively (see FIG. 6).

According to an embodiment, the use of PCAT as the sole active materials or as additives to existing technologies may greatly improve the performance, mechanical or electrical, of energy storage devices.

According to an embodiment, PCAT may also be useful as electrode materials for energy storage device such as, but not limited to, a lithium battery, sodium battery, magnesium battery, aluminium battery, potassium battery, a calcium battery, or a hybrid device combining electrode materials of any of the above devices.

According to an embodiment, due to the nature of organic materials and their ability to undergo redox chemistry with a wide variety of ions in respect to their charge balancing, PCAT may be much more versatile than their inorganic counterparts such as metals oxides that require ions of a specific size and/or charge in order for them to function as electrode materials. This may allow organic materials to be used in a number of different battery configurations and chemistries. The energy storage devices may be constructed to have one or both of flexible mechanical properties and a customizable form factor. Here, flexible mechanical properties refer to the entire energy storage device possessing mechanical flexibility with a bending radius of at least 5 mm and twisting angle of at least 15° while still maintaining greater than 90% of the device performance in an unbent or twisted state.

These materials may also be used for water splitting, taking advantage of the electrocatalytic properties of the materials. This would occur through electrocatalytic oxidation of water in an appropriate electrolytic solution to produce molecular oxygen and/or hydrogen peroxide. This may also occur through the electrocatalytic reduction of water in an appropriate electrolytic solution to produce molecular hydrogen. The inventors contemplate that these materials may be useful as therapeutic agents, for example a drug delivery vessel, a drug, and/or a prodrug. These materials may also be used for water purification and heavy metal recovery. This would occur though a binding of metal ions and impurities to the catechol moiety and/or a change in redox state of the impurity/ metal ion and/or the material.

The foregoing description of the preferred embodiments of the present disclosure have been presented to illustrate the principles of the invention and not to limit the invention to the particular embodiment illustrated. It is intended that the scope of the invention be defined by all of the embodiments encompassed within the following claims and their equivalents. References

Patent Literature

PTL 1 : European Patent Application No. 12811218.2

PTL 2: European Patent Application No. 11753064.2

PTL 3: United States Patent Application No. 14/147,671

PTL 4: PCT/ Canadian Patent Application No. 2017/050114

PTL 5: United States Patent Application No. 2019/0190027 A1

PTL 6: United States Patent Application No. 2014/0308581 A1

PTL 7: United States Patent Application No. 2014/0141322 A1

PTL 8: United States Patent No. US 10,326,138 B2

PTL 9: United States Patent No. US 10,320,001 B2

PTL 10: United States Patent No. US 8,338,028 B2

PTL 11 : United States Patent Application No. 2016/0268607 A1

PTL 12: JP 2013-20760A

Non-patent Literature

Lakraychi, A. E.; Deunf, E.; Fahsi, K.; Jimenez, P.; Bonnet, J. P.; Djedaini- Pilard, F.; Becuwe, M.; Poizot, P.; Dolhem, F. An Air-Stable Lithiated Cathode Material Based on a 1 ,4-Benzenedisulfonate Backbone for Organic Li-Ion Batteries. J. Mater. Chem. A 2018, 6 (39), 19182-19189.

WANG, S.; Wang, L.; Zhang, K.; Zhu, Z.; Tao, Z.; Chen, J. Organic Li 4C 8H 20 6Nanosheets for Lithium-Ion Batteries. Nano Lett. 2013, 13 (9), 4404- 4409.

Claims

THEREFORE WHAT IS CLAIMED IS:

1 . An electroactive material, comprising the molecular structures PCAT:

[PCAT]:

H is hydrogen;

O is oxygen

M is a counter-ion chosen from lithium, sodium, potassium, magnesium, or calcium; n is the number of alkali/hydroxy oxide units ranging from 2 to 4; k is the number of repeating units ranging from 0 to 3; m is the number of repeating units ranging from 1 to 2,000,000.

2. The molecular structures PCAT according to claim 1 , produced using precursors selected from the group consisting of:

where n is an integer in a range from 2 to about 100.

3. The electroactive material according to claim 1 , wherein the aromatic group is any one of the following base structures:

4. The electroactive material according to claim 1 , comprising the molecular structure PCAT1 :

[PCAT1]:

M is a counter-ion comprised of lithium, sodium, potassium, magnesium, or calcium.

5. The electroactive material according to claim 4, wherein M is lithium.

6. The electroactive material according to claim 5, wherein n is 2.

7. The electroactive material according to claim 6, wherein k is 0.

8. The electroactive material according to claim 7, wherein m is 1 .

9. The electroactive material according to claim 6, wherein k is 1 and X is a methylene group.

10. The electroactive material according to claim 9, wherein m is an integer between 1 and 1000.

11 . The electroactive material according to claim 1 , comprising the molecular structure PCAT2:

[PCAT2]:

M is a counter-ion chosen from lithium, sodium, potassium, magnesium, or calcium;

H is hydrogen; and

O is oxygen.

12. The electroactive material according to claim 11 , wherein M is lithium.

13. The electroactive material of claim 12, wherein n is 2.

14. The electroactive material of claim 13, wherein k is 0.

15. The electroactive material of claim 14, wherein m is 1 .

16. The electroactive material of claim 12, wherein k is 1 and X is a methylene group.

17. The electroactive material of claim 16, wherein m is an integer between

1 and 1000.

18. A method of making a subset of PCAT using METHOD 1 :

[METHOD 1]:

R1 is a reagent chosen from formaldehyde or paraformaldehyde;

T1 is a temperature between about -20 and about 250 degrees Celsius; and

P1 is a pressure between about 0.5 and about 20 atmospheres.

19. The method according to claim 18, wherein the aromatic group is any one of the following base structures:

20. A method to make a precursor of a subset of PCAT is synthesized by

Method 2:

[METHOD 2]:

T1 is a temperature between about -20 and about 250 degrees Celsius;

21 . The method according to claim 20, wherein the aromatic group is any one of the following base structures:

22. A method to synthesize PCAT by Method 3:

[METHOD 3]:

T1 is a temperature between about -20 and about 250 degrees Celsius; and P1 is a pressure between about 0.5 and about 20 atmospheres.

23. The method according to claim 22, wherein the aromatic group is any one of the following base structures:

24. An energy storage device made of at least one material according claim

1.

25. The use of an energy storage device of claim 24 as a lithium ion battery, sodium ion battery, magnesium ion battery, aluminium ion battery, potassium ion battery, a calcium battery, or a hybrid device.