Polyaniline-based batteries with lean electrolytes

Abstract

The battery includes a first electrode acting as an anode and a second electrode acting as a cathode, the second electrode including at least one polymer binder, a conductive carbon-based material, and a composite of polyaniline and graphene-based material as an active material. An insulating separator material supporting lithium ion transport is disposed between the first and second electrodes. The battery further includes an electrolyte comprising at least one aprotic solvent and at least one lithium salt soluble in the at least one aprotic solvent.

Description

[Technical field]

[0001] REFERENCE TO RELATED APPLICATIONS This application claims priority under 35 U.S.C. §119(e) to and the benefit of U.S. Provisional Patent Application No. 63 / 312,015, entitled “POLYANILINE BASED BATTERIES WITH LEAN ELECTROLYTE,” filed in the U.S. Patent and Trademark Office on February 20, 2022, the contents of which are incorporated by reference in their entirety as if fully set forth herein.

[0002] The present disclosure relates to rechargeable batteries, and in particular to rechargeable batteries that utilize polyaniline / graphene-based materials as components of the battery cathode. [Background technology]

[0003] A rechargeable battery is a type of secondary battery that can be recharged and used multiple times, making it an environmentally friendly, cost-effective alternative to disposable batteries. Rechargeable batteries are widely used in portable electronic devices, such as smartphones, laptops, and cameras, as well as in larger applications such as electric vehicles and energy storage systems. The most common types of rechargeable batteries are nickel-cadmium (NiCad), nickel-metal hydride (NiMH), and lithium-ion (Li-ion) batteries. Each rechargeable battery has its own characteristics, including energy density, voltage, and discharge rate, making it suitable for different applications. Rechargeable batteries must be properly maintained to ensure their performance and lifespan, including storing them properly, recharging them properly, and using them within their operating temperature range. Lightweight rechargeable batteries with high charge / discharge energy capacity are sought after in autonomy energetics.

[0004] A typical metal-ion battery includes a negative electrode, a positive electrode, and a liquid electrolyte separating the negative and positive electrodes. The electrolyte is a solution containing ions that act as charge carriers between the negative and positive electrodes. When the battery is charged, these ions move through the electrolyte from the negative electrode to the positive electrode, and when the battery is discharged, these ions move in the opposite direction.

[0005] The separator in a liquid electrolyte battery acts as a barrier between the negative and positive electrodes, preventing short circuits while allowing the flow of ions. The separator is a porous material, usually made of polypropylene, that is immersed in the electrolyte, thus allowing the flow of ions while maintaining the structure of the battery. The separator plays an important role in maintaining the stability and safety of the battery, ensuring that it operates smoothly and efficiently.

[0006] The active material of the negative electrode of a lithium-ion battery is usually based on a graphite substrate with a theoretical capacity of 372 mAh / g. The electrolyte usually consists of a solution of the corresponding metal salt or mixture of salts in an organic solvent or mixture of organic solvents. Such liquid electrolyte is usually located in the pores of both the negative and positive electrodes with a separator between them, e.g. polypropylene. The amount and concentration of the liquid electrolyte are responsible for simultaneously providing the lowest battery weight and the highest level of ionic conductivity.

[0007] The cathode active materials are usually based on oxides of lithiated transition metals such as nickel, cobalt, or manganese, or lithium iron phosphate. The theoretical capacity of such cathode active materials is usually disadvantageously about or less than 200 mAh / g (R. Schmuch et al., "Performance and cost of materials for lithium-based rechargeable automotive batteries", Nat. Energy, 2018, vol. 3, p. 267). The cathode active materials based on transition metal compounds have other disadvantageous properties that motivate the urgent need for new cathode active materials that provide significant improvements in battery capacity. (J.-M. Kim et al., "A review on the stability and surface modification of layered transition-metal oxide cathodes", Materials Today, 2021, Vol. 46, p. 155; G.-L. Xu et al., "Challenges and Strategies to Advance High-Energy Nickel-Rich Layered Lithium Transition Metal Oxide Cathodes for Harsh Operation", Adv. Func. Mater., 2020, Vol. 30, p. 2004748; W. Li., "Review-An Unpredictable Hazard in Lithium-ion Batteries from Transition Metal Ions: Dissolution from Cathodes, Deposition on Anodes and Elimination Strategies", J. Electrochem. Soc., 2020, Vol. 167, p. 090514).

[0008] Conductive conjugated polymers are a class of polymers that are both electrically conductive and conjugated. Conjugated polymers are materials that have a repeating pattern of alternating single and double bonds along the polymer backbone. This alternating arrangement allows electrons to move along the polymer chain, resulting in electrical conductivity. Conjugated polymers are also lightweight and flexible, making them ideal for use in wearable devices and flexible electronics. In addition, conjugated polymers have excellent stability and heat resistance, making them suitable for use in high-temperature environments.

[0009] Conductive conjugated polymers can be an alternative to cathode active materials based on transition metal compounds. For example, polyaniline (PANI) is redox active and capable of reversible electrochemical transitions at high potentials. These characteristics make PANI a potential candidate for the active component of battery cathodes (OAKozarenko et al., "Effect of potential range on electrochemical performance of polyaniline as a component of lithium battery electrodes", Electrochim.Acta, 2015, Vol. 184, p. 111).

[0010] Chemically synthesized PANI doped with HCl is known to be characterized by a specific capacity of about 20 mAh / g in a mixture of ethylene carbonate / dimethyl carbonate / 1M LiPF6 electrolyte, which is about 14% of the theoretical capacity of 147 mAh / g using 50% doping of the PANI polymer (KS Ryu et al., "Comparison of lithium / polyaniline secondary batteries with different dopants of HCl and lithium ionic salts", J. Power Sources, 2000, Vol. 88, pp. 197-201; AJ Heeger, "Nobel Lecture: Semiconducting and metallic polymers: The fourth generation of polymeric materials", Rev. Mod. Phys., 2001, Vol. 73, p. 681; AG MacDiarmid, "Synthetic Metals: A Novel Role for Organic Polymers (Nobel Lecture), Angew. Chem. Int. Ed. 2001, Vol. 40, p. 2581; P. Novak et al., "Electrochemically active polymers for rechargeable batteries", Chem. Rev., 1997, Vol. 97, p. 207).

[0011] It is also known that chemically synthesized PANI doped with lithium salts can exhibit a specific capacity of about 100 mAh / g in similar electrolytes, which corresponds to about 70% of the theoretical capacity (KS Ryu et al., "Polyaniline doped with dimethyl sulfate as а polymer electrode for all solid-state power source system", Solid State Ionics, 2004, Vol. 175, p. 759). PANI can also be electrochemically synthesized, with a specific capacity of about 100 mAh / g in organic electrolytes (N. Daifuku et al., "Electric cells utilizing polyaniline as а positive electrode active material", U.S. Patent No. 4,717,634 (1988)).

[0012] Furthermore, lithium salt-doped PANI can be mechanochemically prepared and shows a specific capacity of 146 mAh / g in organic electrolytes. The obtained capacity is almost 100% of the theoretical capacity limit using 50% doping of the polymer (O. Posudievsky et al., "Electrochemical performance of mechanochemically prepared polyaniline doped with lithium salt", Synth. Met., 2012, vol. 162, p. 2206).

[0013] Recently, it has been shown that the doping degree of PANI can exceed 50% (J. Gaubicher et al., "Lithium-Doped Pernigraniline-Based Materials", U.S. Patent No. 10,651,473 (2020)). This is possible because hydrogen atoms bonded to nitrogen in the structure of PANI are replaced by lithium atoms, but the authors emphasize the need for anions to assist in charge / discharge cycling.

[0014] Composites of PANI with graphene-based materials (GBM) showed a significantly larger specific capacity of about 250 mAh / g. The GBM in the PANI / GBM composite is a mixture of mostly multi-, few-, and single-layer graphene particles (O. Posudiievskyi, International Patent Application Serial No. PCT / IB2018 / 055009). However, it should be noted that no evidence of practical long-term charge / discharge cycling of PANI has been shown (see, for example, J. Gaubicher et al., "Lithium-Doped Pernigraniline-Based Materials," U.S. Pat. No. 10,651,473 (2020); O. Posudiievskyi, ibid.). There was a lack of consideration and consideration of the amount of electrolyte required to make PANI-based materials practical for use in batteries, especially lithium battery cathodes, based on the increasing doping levels of PANI.

[0015] On the other hand, doping of PANI with anions during redox transitions at high potentials has been reported (P. Jimenez et al., "Lithium n-Doped Polyaniline as a High-Performance Electroactive Material for Rechargeable Batteries", Angew. Chem., Int. Ed., 2017, Vol. 56, p. 1553; M. Charlton et al., "Polyaniline Electrode Activation in Li Cells", J. Electrochem. Soc., 2020, Vol. 167, p. 080501).

[0016] The minimum amount of anion required for 50% doping of PANI has been reported to be equivalent to one anion per two CHN polymer units, 1 mole of anion per approximately 182 g of polymer, or 1 L of commonly used liquid organic electrolyte with a lithium salt concentration of 1 M per approximately 182 g of polymer (Y. Yamada et al., “Advances and issues in developing salt concentrated battery electrolytes”, Nat. Energy, 2019, Vol. 4, p. 269).

[0017] Thus, about 5.5 mL of electrolyte is required for about 1 g of polymer in the cathode material, or about 5.5 g of electrolyte for the theoretical charge storage limit of the polymer, 147 mAh capacity. The ratio of electrolyte weight to cathode capacity (E / C) for such a system is equal to 37.4 g / (Ah). Such high E / C values ​​suggest severe limitations, if not impracticality, for PANI-based cathodes in high-performance metal-ion batteries. In fact, practical lithium-ion batteries have demonstrated E / C ratios of less than 3 g / (Ah) (X. Ren et al., "Enabling High-Voltage Lithium-Metal Batteries under Practical Conditions," Joule, 2019, vol. 3, p. 1662; Sh. Chen et al., "Critical Parameters for Evaluating Coin Cells and Pouch Cells of Rechargeable Li-Metal Batteries," Joule, 2019, vol. 3, p. 1094; J. Liu et al., "Pathways for practical high-energy long-cycling lithium metal batteries," Nat. Energy, 2019, vol. 4, p. 180; H. Li., "Practical Evaluation of Li-Ion Batteries," Joule, 2019, vol. 3, p. 911).

[0018] It is theorized that charge / discharge cycling of the anion-doped PANI allows for even higher E / C values ​​(compared to 37.4 g / (Ah) for 50% doped PANI), resulting in a higher specific capacity for PANI in the battery cathode. [Prior art documents] [Patent documents]

[0019] [Patent Document 1] U.S. Patent No. 4,717,634 [Patent Document 2] U.S. Patent No. 10,651,473 [Patent Document 3] PCT / IB2018 / 055009 issue [Patent Document 4] U.S. Patent No. 10,651,473 [Patent Document 5] U.S. Patent Application Serial No. 12 / 623,000 [Non-patent literature]

[0020] [Non-Patent Document 1] R. Schmuch et al., "Performance and cost of materials for lithium-based rechargeable automotive batteries," Nat. Energy, 2018, Vol. 3, p. 267 [Non-Patent Document 2] J.-M. Kim et al., "A review on the stability and surface modification of layered transition-metal oxide cathodes," Materials Today, 2021, Vol. 46, p. 155 [Non-Patent Document 3] G.-L. Xu et al., "Challenges and Strategies to Advance High-Energy Nickel-Rich Layered Lithium Transition Metal Oxide Cathodes for Harsh Operation," Adv. Func. Mater., 2020, vol. 30, pp. 2004748. [Non-Patent Document 4] W.Li., "Review-An Unpredictable Hazard in Lithium-ion Batteries from Transition Metal Ions: Dissolution from Cathodes,Deposition on Anodes and Elimination Strategies", J.Electrochem.Soc., 2020, vol. 167, p. 090514 [Non-Patent Document 5] OAKozarenko et al., “Effect of potential range on electrochemical performance of polyaniline as a component of lithium battery electrodes”, Electrochim.Acta, 2015, vol. 184, p. 111 [Non-Patent Document 6] KS Ryu et al., "Comparison of lithium / polyaniline secondary batteries with different dopants of HCl and lithium ionic salts," J. Power Sources, 2000, Vol. 88, pp. 197-201 [Non-Patent Document 7] AJ Heeger, "Nobel Lecture: Semiconducting and metallic polymers: The fourth generation of polymeric materials", Rev. Mod. Phys., 2001, vol. 73, p. 681. [Non-Patent Document 8] AGMacDiarmid, "Synthetic Metals: A Novel Role for Organic Polymers (Nobel Lecture)", Angew.Chem.Int.Ed.2001, vol. 40, p. 2581 [Non-Patent Document 9] P. Novak et al., "Electrochemically active polymers for rechargeable batteries," Chem. Rev., 1997, Vol. 97, p. 207 [Non-Patent Document 10] KS Ryu et al., "Polyaniline doped with dimethyl sulfate as a polymer electrode for all solid-state power source system," Solid State Ionics, 2004, Vol. 175, p. 759 [Non-Patent Document 11] O. Posudievsky et al., “Electrochemical performance of mechanochemically prepared polyaniline doped with lithium salt”, Synth.Met., 2012, vol. 162, p. 2206 [Non-Patent Document 12] P. Jimenez et al., "Lithium n-Doped Polyaniline as a High-Performance Electroactive Material for Rechargeable Batteries," Angew. Chem., Int. Ed., 2017, Vol. 56, p. 1553 [Non-Patent Document 13] M. Charlton et al., "Polyaniline Electrode Activation in Li Cells," J. Electrochem. Soc., 2020, Vol. 167, p. 080501 [Non-Patent Document 14] Y. Yamada et al., "Advances and issues in developing salt concentrated battery electrolytes," Nat. Energy, 2019, Vol. 4, p. 269 [Non-Patent Document 15] X. Ren et al., "Enabling High-Voltage Lithium-Metal Batteries under Practical Conditions," Joule, 2019, Vol. 3, p. 1662 [Non-Patent Document 16] Sh. Chen et al., "Critical Parameters for Evaluating Coin Cells and Pouch Cells of Rechargeable Li-Metal Batteries," Joule, 2019, Vol. 3, p. 1094 [Non-Patent Document 17] J. Liu et al., "Pathways for practical high-energy long-cycling lithium metal batteries", Nat.Energy, 2019, vol. 4, p. 180 [Non-Patent Document 18] H.Li., "Practical Evaluation of Li-Ion Batteries", Joule, 2019, vol. 3, p. 911 [Non-Patent Document 19] J. Gao et al., “Lithiated Nafion as polymer electrolyte for solid-state lithium sulfur batteries using carbon-sulfur composite cathode”, J. Power Sources, 2018, vol. 382, ​​p. 179 Summary of the Invention [Problem to be solved by the invention]

[0021] In general, systems and methods are disclosed that establish a new mechanism for the charge / discharge process of PANI that is free of anion participation and is based on reversible insertion / extraction of cations. The disclosed systems and methods provide long-term reversible charge / discharge cycling of PANI suitable for practical rechargeable batteries, while resolving the problem of large amounts of electrolyte previously thought to be required for PANI to function.

[0022] The disclosed mechanism suggests that batteries utilizing PANI as the positive electrode active component may function like a rocking chair. A practical consequence of constant electrolyte concentration is that the metal ion conductivity between the electrodes in the battery is maximized as the electrode pores are filled, leading to highly efficient metal ion transport. A minimal amount of electrolyte sufficient to fill the positive electrode pores achieves an E / C ratio of less than 3 g / (Ah), as in the best commercial lithium-ion batteries. [Means for solving the problem]

[0023] In a first general embodiment, a battery is disclosed. The battery includes a first electrode acting as a negative electrode and a second electrode acting as a positive electrode. The second electrode includes at least one polymer binder, a conductive carbon-based material, and an active material. The battery further includes an insulating separator material disposed between the first and second electrodes and supporting the transport of lithium ions, and an electrolyte including at least one aprotic solvent and at least one lithium salt soluble in the at least one aprotic solvent.

[0024] In one embodiment, the battery includes an amount of electrolyte corresponding to a ratio of electrolyte weight to positive electrode capacity: in a first example, the ratio is less than 10 g / (Ah), and in a second example, the ratio is less than 3 g / (Ah).

[0025] In one embodiment, the first electrode is made of lithium metal, a lithium alloy, graphite, a material containing graphene, silicon, or SiO xIn one embodiment, the active material comprises a composite of polyaniline and a graphene-based material.

[0026] In one embodiment, the electrolyte is liquid and non-aqueous, hi an alternative embodiment, the electrolyte is a solid comprising a lithium ion organic polymer or a lithium ion conducting inorganic compound.

[0027] In a second general aspect, a method of manufacturing a battery is disclosed. The method includes providing a first electrode acting as a negative electrode and a second electrode acting as a positive electrode, the second electrode including at least one polymer binder, a conductive carbon-based material, and an active material. The method includes disposing an insulating separator material between the first and second electrodes that supports lithium ion transport. The method further includes providing an electrolyte between the first and second electrodes that includes at least one aprotic solvent and at least one lithium salt soluble in the at least one aprotic solvent.

[0028] In one embodiment of the method, the active material comprises a composite of polyaniline and graphene based material. In a related embodiment, the composite of polyaniline and graphene based material is prepared according to a process that includes grinding a mixture of emeraldine base state polyaniline and graphene based material in a relative weight ratio. In one embodiment, the relative weight ratio is from about 75:25 polyaniline to graphene based material to about 99:1 polyaniline to graphene based material.

[0029] In one embodiment of the method, the grinding is performed in a solvent-free environment. In one embodiment of the method, the graphene-based material comprises a mixture of multi-layer, few-layer, and single-layer graphene particles. The mixture may be prepared by chemical, mechanochemical, electrochemical, sonochemical, or thermochemical exfoliation of particles of graphite, graphene oxide, intercalated graphite, or expanded graphite.

[0030] In one embodiment of the method, the method further comprises the optional step of isolating and purifying the polyaniline / graphene based composite from other materials present during the grinding process.

[0031] In one embodiment of the method, the first electrode is formed by a deposition step that includes depositing a cathode material on a current collector, the cathode material including a binder, a conductive additive, and an active material. In a related embodiment, the binder is water soluble. In a further related embodiment, the binder is polyethylene oxide, styrene-butadiene rubber, alginate, polyacrylic acid, chitosan and its water soluble derivatives, resins, amphiphilic and rubber latexes, polyolefin grafted acrylic acid copolymers, carboxymethyl cellulose, β-cyclodextrin, or combinations thereof.

[0032] In one embodiment of the method, the depositing step includes preparing a slurry of the cathode material by mixing the binder, the conductive additive, and the active material with water. In a related embodiment, the slurry is free of N-methylpyrrolidone.

[0033] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art.Methods and materials similar or equivalent to those described herein can be used in carrying out or testing any of the described embodiments, but suitable methods and materials are described below.In addition, materials, methods, and examples are illustrative only and are not intended to be limiting.In the event of any discrepancy with terms used in the art, the present specification, including definitions, shall govern.

[0034] The foregoing summary is illustrative only and is not intended to be in any way limiting. In addition to the exemplary aspects, embodiments, and features described above, further aspects, embodiments, and features will become apparent by reference to the drawings and the following detailed description and claims.

[0035] The present embodiments are illustrated by the figures of the accompanying drawings, which may not necessarily be to scale and in which like reference symbols indicate similar elements. [Brief description of the drawings]

[0036] [Figure 1] FIG. 1 shows a cross-section of a rechargeable battery using a PANI-based cathode according to one embodiment. [Diagram 2] 1 is a plot of specific capacity versus cycle number for two different cells, each having a different PANI-based cathode. [Diagram 3] 3 is a graph showing potential versus discharge capacity for cell 1 of the graph in FIG. 2. [Figure 4] 1 is a graph plotting specific capacity versus cycle number for two different cells, according to one embodiment. [Diagram 5] 1 is a plot of specific capacity versus cycle number for a cell according to one embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0037] FIG. 1 is an exemplary cross-sectional view of a rechargeable battery 1 according to one embodiment. In this embodiment, PANI is utilized as the active component of the positive electrode. In this embodiment, the rechargeable battery 1 includes an anode layer 2, an electrolyte layer 3, and a cathode layer 4. The anode layer 2 can be composed of a common anode material, such as, but not limited to, lithium or a lithium alloy, or a composite containing lithium. The anode 2 can be composed of a non-lithium material as the active component, such as, but not limited to, graphite, graphene-based materials, silicon, SiO x The material may be made of any of a number of materials, including graphite, graphene, silicon, or SiO x It should be understood that lithiated forms of materials should be used when these materials do not contain the amount of lithium metal or lithium ions required for optimum battery performance.

[0038] In this embodiment, the electrolyte layer 3 is a porous polymeric membrane, the pores of which are filled with: 1) a liquid electrolyte, which is a solution of one or more lithium salts in an organic aprotic solvent or a mixture of different aprotic solvents, and preferably an additive that serves to improve the electrode-electrolyte interface; 2) an organic polymer film that has lithium ion conductivity at the optimal concentration of the corresponding lithium salt (e.g., for polyethylene oxide, the optimal ratio of oxygen to lithium is about 8:1); 3) a lithiated NAFION or similar film that has intrinsic lithium ion conductivity; 4) a lithium ion conducting solid inorganic electrolyte; or 5) a combination of any or all of the preceding items 1-5.

[0039] In this embodiment, the positive electrode layer 4 contains as active components the PANI and GBM based composite disclosed in International Patent Application Serial No. PCT / IB2018 / 055009, which is incorporated herein by reference in its entirety. In this embodiment, the positive electrode layer 4 is composed of a solvent-free mechanochemically prepared PANI / GBM composite containing emeraldine base PANI and a mixture of multi-layer, few-layer, and single-layer graphene particles as GMB. The mechanochemical procedure for preparing PANI / GBM is essentially similar to the mechanochemical procedure for preparing hybrid nanocomposites disclosed in O. Posudievsky et al., "Hybrid Two-and Three-Component Host-Guest Nanocomposites and Method for Manufacturing the Same," U.S. Patent Application Serial No. 12 / 623,000 to GM Global Technology Operations, Inc., which is incorporated herein by reference in its entirety.

[0040] The rechargeable battery 1 was shown to have rocking chair functionality (e.g., charge / discharge cycling to induce cation insertion / extraction) utilizing a lithium metal anode; an electrolyte layer composed of a lithiated NAFION (LIFION) membrane free of any soluble lithium salts, e.g., LiBF4, LiClO4, LiPF6, etc.; and a PANI-based cathode. The rechargeable battery 1 was assembled in a CR2016 cell in an argon-filled MBRAUN glovebox with oxygen and water content less than 0.1 ppm.

[0041] In this example, the lithium anode was made from Li foil. The LIFION membrane was prepared from a commercially available NAFION membrane according to a known method (J. Gao et al., "Lithiated Nafion as polymer electrolyte for solid-state lithium sulfur batteries using carbon-sulfur composite cathode", J. Power Sources, 2018, Vol. 382, ​​p. 179). Before assembling the CR2016 cell, the LIFION membrane was soaked in anhydrous propylene carbonate.

[0042] To investigate the properties of the rechargeable battery 1, several cells were fabricated. The first cell, "Cell I", contained a cathode material formed from a PANI and GBM based composite prepared mechanochemically according to the procedure described in International Patent Application Serial No. PCT / IB2018 / 055009, with a weight ratio of PANI to GBM equal to about 9:1, a polymer binder, and a carbon black additive. The weight ratio of the cathode material components was 85:10:5 (PANI / GBM:polymer binder:carbon black additive). In this example, the polymer binder was a mixture of polyolefin grafted acrylic acid copolymer (3 wt% aqueous solution) and carboxymethyl cellulose (2.5 wt% aqueous solution) in a 1:3 ratio. In this example, a cathode material slurry was prepared using double distilled water and deposited on a cathode current collector using a doctor blade. The cathode material was dried in air at 60°C and then under vacuum at 80°C. The cathode material loading was 3 mAh / cm2 This was done to ensure a single-sided capacity of 1000m.

[0043] The second cell, “Cell II,” was prepared in a similar manner to Cell I, except that pure emeraldine base PANI was used instead of the PANI / GBM complex.

[0044] The third and fourth cells (cell III and cell IV, respectively) were constructed to investigate the maximum specific capacity of PANI and its feasibility of achieving practical long-term operation of lithium metal batteries.

[0045] In these examples, Cell III samples were assembled using a procedure similar to that of Cell I samples, except that the electrolyte layer was made from a Celgard 2400 polypropylene membrane (Celgard, LLC, Charlotte, NC, USA) and a 1 M LiClO4 solution in propylene carbonate, as opposed to the LIFION membrane and pure propylene carbonate utilized in Cell I.

[0046] The sample of Cell IV was assembled in a similar manner to that of Cell III, except that polyvinylidene fluoride (PVDF) binder and N-methyl-2-pyrrolidone (NMP) were used as the solvent in preparing the slurry for depositing the PANI / GBM-based cathode material on the cathode current collector.

[0047] Referring now to FIG. 2, in this embodiment, the cycling data shows an increase in the electrochemical activity of PANI in Cell I. FIG. 2 clearly demonstrates that PANI can sustain charge / discharge cycles in the absence of mobile anions in the electrolyte. Without wishing to be bound by theory, it is believed that the only anions in the electrolyte are SO2 immobilized in the LIFION framework by covalent bonds. 3-Again, without wishing to be bound by theory, it is presumed that the steady increase in the specific capacity of PANI is due to the gradual lithiation of the nitrogen atoms in its structure, since the doping / dedoping of PANI in a cycling cell can only proceed with the participation of lithium cations, and these ions are the only mobile ions contained in the electrolyte.

[0048] Figure 2 also clearly demonstrates that the PANI in the positive electrode of Cell I can efficiently conduct lithium ions, since without this property, PANI would not be able to sustain the progressive increase in its specific capacity during charge-discharge cycling up to nearly 100% doping level.

[0049] Figure 2 further demonstrates that the efficient functioning of PANI as the active component of the positive electrode in Cell I is due to the presence and effect of GBM, since in the absence of GBM particles (and thus in the absence of interactions between GBM particles and PANI polymers), the specific capacity of PANI in Cell II, which does not contain GBM in its cathode material composition, is almost 16 times lower.

[0050] Referring now to FIG. 3, the charge-discharge cycling data of cell I are shown. After multiple charge-discharge cycles, PANI has a specific capacity of about 285 mAh / g, which corresponds to nearly 100% doping at high potential. This result is achieved without the use of any lithium salt dissolved in the electrolyte, or even in the battery at all. The conclusion from these data is that in high performance PANI-based batteries, a minimal amount of organic solvent is required to fill the pores of the anode, cathode, and separator. Optionally, a small amount of lithium salt can be dissolved in an organic aprotic solvent as a component of the electrolyte to ensure a light battery weight and provide the required level of ionic conductivity at the same time. These data indicate that PANI-based alkali metal and metal ion, particularly lithium and lithium ion batteries with lean electrolytes and E / C less than 3 g / (Ah) perform as well as or better than known commercial lithium ion batteries.

[0051] Now, looking at Figures 4 and 5, it can be seen that the PANI in Cell III features a higher specific capacity of about 285 mAh / g compared to Cell I and Cell IV. In addition, Figure 4 shows that the common binder (PVDF) and common solvent (NMP) for preparing the cathode material slurry for Cell IV are not applicable in the case of the PANI / GBM composite cathode material because NMP partially dissolves PANI. The degradation of PANI may destroy the interaction between PANI and GBM, thus precluding the progress of the new doping mechanism of PANI, limiting the specific capacity of Cell IV to a value close to 50% doping. It should be noted that the cathode material in PCT / IB2018 / 055009 was fabricated using poly[(vinylidene fluoride)-co-hexafluoropropylene] as a binder and acetylene as a solvent for slurry preparation for depositing the PANI / GBM composite-based cathode material on the cathode current collector, and the specific capacity of the resulting PANI was about 250 mAh / g.

[0052] At the same time, a solution of water-soluble binder, such as polyacrylic acid and carboxymethyl cellulose dissolved in water, can be used to prepare the cathode material slurry, resulting in a larger specific capacity of PANI and a longer cycle of the PANI-based lithium metal battery, while ensuring a lower cost for preparing and processing the cathode material, and reducing the amount of organic solvents used, which have ecological and environmental hazards associated with battery production.

[0053] Although several exemplary embodiments have been described, it will be understood that various modifications can be made without departing from the spirit and scope of the various embodiments presented herein. Accordingly, other embodiments are within the scope of the following claims.

Claims

1. a first electrode acting as a negative electrode and including a lithium source; a second electrode acting as a positive electrode and comprising at least one polymer binder, a conductive carbon-based material, and an active material; an electrolyte disposed between the first and second electrodes and supporting the transport of lithium ions; the active material is obtained by pulverizing a mixture of emeraldine base polyaniline and a graphene-based material in a relative weight ratio; The lithium ion battery, wherein the first electrode, the second electrode, and the electrolyte are operatively assembled to function as a rocking chair lithium ion battery.

2. 10. The lithium ion battery of claim 1, comprising an amount of said electrolyte corresponding to a ratio of electrolyte weight to positive electrode capacity.

3. 3. The lithium ion battery of claim 2, wherein the ratio is less than 10 g / (Ah).

4. The electrolyte is a non-aqueous liquid electrolyte, or 10. The lithium ion battery of claim 1, wherein the lithium ion conducting solid is a lithium ion conducting solid.

5. A lithium ion battery as described in claim 4, wherein the non-aqueous liquid electrolyte comprises at least one aprotic solvent and at least one lithium salt that is soluble in the at least one non-protonic solvent.

6. A lithium ion battery as described in claim 4, wherein the lithium ion conductive solid electrolyte comprises a lithium ion conductive organic polymer or a lithium ion conductive solid inorganic compound.

7. 1. A method of manufacturing a battery, comprising: Providing a first electrode that acts as a negative electrode; providing a second electrode to act as a positive electrode, said second electrode comprising at least one polymer binder, a conductive carbon-based material, and an active material; disposing an electrolyte between the first and second electrodes; the active material includes a composite including polyaniline and a graphene-based material; The method, wherein the composite comprising polyaniline and a graphene-based material is prepared according to a process comprising grinding a mixture of emeraldine base state polyaniline and a graphene-based material in a relative weight ratio.

8. The method of claim 7 , wherein the milling is carried out in a solvent-free environment.

9. 8. The method of claim 7, wherein the graphene-based material comprises a mixture of multi-layer, few-layer, and single-layer graphene particles.

10. 8. The method of claim 7, wherein the relative weight ratio is from about 75:25 polyaniline to graphene based material to about 99:1 polyaniline to graphene based material.

11. 8. The method of claim 7, further comprising the optional step of isolating and purifying the polyaniline / graphene-based composite from other materials present during the grinding process.

12. 8. The method of claim 7, wherein the second electrode is formed by a depositing step comprising depositing a cathode material on a current collector, the cathode material comprising a binder, a conductive additive, and the active material.

13. The method of claim 12 , wherein the binder is water-soluble.

14. 13. The method of claim 12, wherein the depositing step includes preparing a slurry of the cathode material by mixing the binder, the conductive additive, and the active material with water.

15. 13. The method of claim 12, wherein the binder is polyethylene oxide, styrene-butadiene rubber, alginate, polyacrylic acid, chitosan and its water-soluble derivatives, resins, amphiphilic and rubber latex, polyolefin-grafted acrylic acid copolymers, carboxymethyl cellulose, β-cyclodextrin, or combinations thereof.

16. The method described in claim 12, wherein the depositing step includes preparing a slurry of the positive electrode material by grinding the binder, the conductive additive, and the active material in a solvent-free environment.

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