CN103904356A - Chargable chemical energy-storage device and application thereof - Google Patents

Abstract

The invention discloses a rechargeable chemical energy storage device and its application. The positive electrode of the energy storage device adopts an organic material capable of anion X ^- doping/dedoping, and the negative electrode adopts an organic or organic material capable of cation M ⁺ intercalation/extraction. Inorganic materials, the electrolyte is an aqueous solution with a high salt concentration, a non-aqueous organic solution or a molten salt system, in which the mass fraction of the solute MX reaches 80-110% of the mass fraction in its saturated solution. The invention utilizes the difference in the state and potential of the reversible combination of solute salt anions and cations with the positive and negative electrodes in the electrolyte, and realizes reversible charging and discharging through gain and loss of electrons. The rechargeable chemical energy storage device of the present invention has the characteristics of high power density, long life, high safety, and low cost. Fields that do not require high energy density.

Description

A kind of rechargeable chemical energy storage device and its application

technical field

The invention relates to a rechargeable chemical energy storage device and its application, in particular to a rechargeable chemical energy storage device based on an organic or inorganic electrode material in an aqueous or non-aqueous organic electrolyte system and its application.

Background technique

Lithium-ion batteries, as a rechargeable chemical energy storage device with high energy storage density and power density, have been widely used in portable electronic devices and will be widely used in electric vehicles. The advantage of lithium-ion batteries is their high energy density (80-230Wh/kg). The energy storage mechanism of lithium-ion batteries is to store lithium ions and electrons in the lattice of the material. Since the diffusion of ions in the solid phase at low temperature and room temperature is a rate-controlling step, the power characteristics of lithium-ion batteries are generally less than 3C. Repeated entry and exit of ions in the lattice can easily cause expansion and contraction of the lattice, resulting in uneven stress distribution and cracks in the material, thus affecting the cycle performance. Thirdly, due to the limited reserves of lithium resources in the world, lithium-ion batteries are widely used in electric vehicles and smart grids, and the recycling of lithium-ion batteries is economical, which will inevitably lead to rising costs of lithium-ion batteries and resource shortages and unsustainability. In addition, at present, lithium-ion batteries mainly use organic liquid or polymer electrolytes, and there are major safety hazards in the process of overcharging, overdischarging, or high-current charging and discharging.

Therefore, a new rechargeable chemical energy storage device system with high power density, long life, high safety, low cost and certain energy density is an important development direction of large-scale energy storage batteries.

Compared with traditional inorganic materials, organic materials have a wide range of sources (can be synthesized from various biomass), no precious metals, simple synthesis process, no need for high-temperature sintering, low energy consumption, low cost, high capacity (corresponding to multiple electron transfer), etc. , and easy to recycle.

Compared with global lithium resources, sodium has similar physical and chemical properties to lithium, is abundant in reserves, widely distributed, and costs about one-twentieth of lithium.

Organic electrode materials can have different energy storage mechanisms than the embedded inorganic electrode materials in conventional Li-ion batteries. During the doping/dedoping of anions and the intercalation/extraction of cations, the organic positive and negative electrodes store electricity according to the difference in the potential of gaining and losing electrons of the functional groups in the organic materials of the positive and negative electrodes. During the charge and discharge process, the anions and cations of the solute salt in the electrolyte perform reversible doping/dedoping of anions and intercalation/extraction of cations between the positive and negative electrodes, respectively.

Therefore, the development of new rechargeable chemical energy storage devices based on organic electrode material systems or organic and inorganic combinations with high power density, long life, high safety, low cost and certain energy density (preferably sodium ion rechargeable chemical energy storage devices) Energy devices) have a wide range of commercial value and significance.

Contents of the invention

The purpose of the present invention is to provide a new rechargeable chemical energy storage device with high power density, long life, high safety, low cost and certain energy density.

The principle of the rechargeable chemical energy storage device provided by the present invention is as follows: the positive electrode is an organic material capable of anion X ^- doping/dedoping; the negative electrode is an organic or inorganic material capable of cation M ⁺ intercalation/extraction; electrolyte solution It is an aqueous solution with a high salt concentration, a non-aqueous organic solvent or a molten salt system in which the mass fraction of the solute MX reaches 80-110% of the mass fraction in its saturated solution. When charging, X ^- in the electrolyte is combined with the positive electrode, and M ⁺ is embedded in the negative electrode; when discharging, X ^- is separated from the positive electrode and enters the electrolyte, and M ⁺ comes out of the negative electrode and enters the electrolyte, releasing electrical energy at the same time. The anions and cations in the electrolyte are combined and intercalated with the positive and negative materials respectively, which can be one or more mixed chemical bonds such as covalent, ionic, hydrogen bonds, or weak electrostatic interactions.

The principle of the rechargeable chemical energy storage device described in the present invention is different from traditional "rocking chair" lithium-ion batteries and sodium-ion batteries. The electrolyte in the traditional "rocking chair" lithium-ion battery only serves to connect the positive and negative electrodes, and is the medium for lithium ions to and fro transport between the positive and negative electrodes, and does not participate in the energy storage process (lithium-ion batteries rely on the positive or negative electrodes during charging and discharging). The transition metal elements in the negative electrode material store energy in different chemical valence states). The secondary battery of the present invention utilizes the difference in the states and potentials of the combination of solute salt anions and cations with the positive and negative electrodes respectively in the electrolyte, and realizes charging and discharging through gain and loss of electrons. The solute salt anions and cations in the electrolyte participate in the reversible binding/debonding process of the positive and negative electrodes respectively, realizing reversible charge and discharge. The electrode material has high structural stability and rate performance during the cycle. The secondary energy storage battery can select positive electrode materials free of lithium source and transition metal, further reducing battery cost.

The rechargeable chemical energy storage device of the present invention is different from traditional capacitors and traditional lithium-ion batteries. The differential dE/dQ value of the voltage E and the electric quantity Q during the charging and discharging process may not be constant or equal to zero (capacitor characteristics: dE/dQ= A non-zero constant, lithium-ion battery characteristics: dE/dQ can be zero).

The rechargeable chemical energy storage device of the present invention has a positive electrode, a negative electrode, a diaphragm and an electrolyte, wherein the electrolyte is an aqueous solution with a high salt concentration in which the mass fraction of the solute MX reaches 80-110% of the mass fraction in its saturated solution, non- Water organic solvent or molten salt system.

The positive electrode material described in the present invention is an organic material capable of anionic X ^- doping/dedoping, such as p-type organic polymers, free radical organics, non-conjugated organics, conductive polymers, or organic salts or inorganic porous Materials etc., preferred non-limiting examples are: poly-2,2,6,6-tetramethylpiperidinyl nitroxide-4-yl acrylamide (PTAm, number P _ca 1), poly-2,2 ,6,6-tetramethylpiperidinyl nitroxide-4-yl methyl methacrylate (PTMA, code P _ca 2), poly-1-oxo-2,2,6,6-tetramethyl Base-piperidin-4-yl glycidyl ether (PTGE, code P _ca 3), poly-2,2,6,6-tetramethylpiperidinyl nitroxide-4-vinyl ether (PTVE, No. P _ca 4), polyalkyne-2,2,6,6-tetramethyl-1-piperidinyl nitroxide-4-yl methyl p-benzoate (No. P _ca 5), poly-naphthalene [1,8-cd:4,5-c'd'][1,2]dithialo[dimethyl tetrathiofumarate] (code P _ca 6), poly N-vinyl Carbazole (number P _ca 7), polytriphenylamine (number P _ca 8), polyaniline (PANI, number P _ca 9), aniline/o-nitroaniline copolymer, poly-2,2,5, 5-Tetramethyl-1-pyrrole nitroxide radical-3-ylpropiolate methyl ester (code P _ca 10), polyyne-2,2,6,6-tetramethylpiperidine nitroxide radical -4-yl-4-ylglycidyl ether ether (coded as P _ca 11), polypyrrole (PPy, coded as P _ca 12), or compound, multi-stage polymerization, salt or group substitution of the above compounds, See attached table 1 for its molecular structure formula. When making the positive electrode, conductive materials (such as graphite, carbon tubes, acetylene black, metal powder, conductive polymers or other organic functional molecules that improve electron or ion transport) and binders (such as polyvinylidene fluoride PVDF, Polytetrafluoroethylene PTFE, cellulose CMC, water-soluble rubber SBR or other polymers), the above materials are mixed and evenly coated on stainless steel, Al foil, Ti foil, carbon felt, carbon cloth and other current collectors or pressed into sheets as the positive electrode.

The negative electrode material of the present invention is an organic material or an intercalation-type inorganic material that can carry out cation M ⁺ intercalation/extraction (the preferred M ⁺ ion of the aqueous electrolyte is Na ⁺ ), such as n-type organic polymers, main chain type sulfur-containing Organic polymers, polysulfide polymers, organic carbonyl compounds, conductive polymers or inorganic porous materials, etc. Preferred non-limiting examples are: 1,4,5,8-naphthalene tetracarboxylic anhydride-polyimide (NTCDA-PI, code P _an 1), poly-2,2'-dithioaniline (PDTDA, code P _an 2), poly α, α'-dithio-3-amino-o-xylene (PDTAn, number P _an 3), poly disulfide-2,5-dimercapto-1,3,4 -thiadiazole (PDMcT, number P _an 4), polyquinone (number P _an 5), poly-5-amino-1,4-naphthoquinone (number P _an 6), polyparaphenylene-3, 5-diamino-1,2,4-dithia (PPT, number P _an 7), poly-4,6-dihydro-1H-[1,2]dithio[4,5-c] Pyrrole (MPY, number P _an 8), polytrisulfide-2,5-dimercapto-1,3,4-thiadiazole (number P _an 9), poly-5,8-dihydro-1H, 4H-2,3,6,7-tetrasulfanthracene (code P _an 10), disodium terephthalate (Na ₂ C ₈ H ₄ O ₄ ) (code P _an 11), etc., or the above compounds Composite, multi-level polymerization, salt or group substitution, etc., the molecular structure formula is shown in Attached Table 1; or embedded inorganic materials such as graphite (number P _an 12), Li ₄ Ti ₅ O ₁₂ , NaTi ₂ (PO ₄ ) ₃ . When making the negative electrode, conductive materials (such as graphite, carbon tubes, acetylene black, metal powder, conductive polymers or other organic functional molecules that improve electron or ion transport) and binders (such as polyvinylidene fluoride PVDF, Polytetrafluoroethylene PTFE, cellulose CMC, water-soluble rubber SBR or other polymers), the above materials are mixed and evenly coated on stainless steel, Al foil, Cu foil, Ti foil, carbon felt, carbon cloth collector or pressed into sheets as negative electrode.

The solute salt anion and cation in the electrolyte solution of the present invention respectively participate in the reversible combination process of the positive electrode and the negative electrode, so as to realize reversible charging and discharging, and store electric energy. In order to achieve higher energy density, the electrolyte is selected as an aqueous or non-aqueous organic electrolyte or molten salt body with a high solute salt concentration.

The electrolyte solution of the present invention can be selected from water system or non-aqueous organic system electrolyte according to different positive and negative electrode materials. Among them, the water-based electrolyte may be non-limiting: NaNO ₃ , NaCl, Na ₂ SO ₄ , NaOH, NaBF ₄ , NaPF ₆ , NaClO ₄ - An aqueous solution of one or more sodium salts. The non-aqueous organic electrolyte can be preferably non-limiting: NaBF ₄ , NaPF ₆ , NaClO ₄ , NaFSI, NaTFSI, LiBF ₄ , LiPF ₆ , LiTFSI with the mass fraction of the solute MX reaching 80-110% of the mass fraction in the saturated solution , LiFSI one or more organic salts dissolved in ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), tetrahydrofuran (THF), dimethoxy Ethane (DME), diglyme (DG), diethylene glycol dimethyl ether (DGDME), triethylene glycol dimethyl ether (TGDME), tetraethylene glycol dimethyl ether (TEGDME ), 1,3-dioxolane (DOL), 4-methyl-1,3-dioxolane (4-MeDOL), γ-butyrolactone (γ-BL), methyl formate ( MF), methyl acetate (MA), ethyl acetate (EA), methyl propionate (MP), ethyl propionate (EP), acetonitrile, propionitrile, malononitrile, 3-methoxypropionitrile One or more mixed solvents, molten salt system (e-melt of NaFSI/KFSI or LiFSI/KFSI).

In the electrolyte of the water system or non-aqueous organic system described in the present invention, other supporting electrolytes can also be added, so that the electrolyte of the secondary energy storage battery described in the present invention still has a higher electrical conductivity in the charged final state, Specifically, such as: electrolyte salt containing K ⁺ and N(C ₄ H ₉ ) ₄ ⁺ . The definition of supporting electrolyte is: at least one of the anion and cation of the solute salt in the electrolyte does not participate in the combination/decombination process with the positive and negative electrodes, and its concentration range is 0.01M~1M.

The rechargeable chemical energy storage device provided by the present invention can also add electrolyte salt when making the positive and negative pole pieces. When the rechargeable chemical energy storage device is in the final charging state, the anions and cations in the electrolyte are combined with the positive and negative electrodes, and the electrolyte The conductivity decreases, and the electrolyte salt in the positive and negative electrodes dissolves into the electrolyte to increase the conductivity of the electrolyte in the charged state to reduce the electric field polarization inside the battery caused by the decrease in the conductivity of the electrolyte in the final state of charge.

The rechargeable chemical energy storage device provided by the present invention has a different energy storage mechanism from traditional lithium-ion or sodium-ion secondary batteries or capacitors, and has high power density, long life, and high safety (organic materials are more stable than inorganic materials in the process of over-discharging). The heat released by the material is small; and the ionic conductivity of the electrolyte of the rechargeable chemical energy storage device decreases after charging, there is no damage to the material structure caused by overcharging; there is also no problem of over-discharging), low cost and a certain energy density Our new rechargeable chemical energy storage device (as shown in Figure 2) is a green power source with a wide range of uses, and can be applied to solar power generation, wind power generation, distributed power stations, smart buildings, smart grids and other scales according to the battery structure Energy storage, as well as large-scale energy storage fields such as data centers, communication base stations, industrial energy storage, and national security.

Description of drawings

Hereinafter, embodiments of the present invention will be described in detail in conjunction with the accompanying drawings, wherein:

Figure 1 is a working principle diagram of a rechargeable chemical energy storage device;

Figure 2 is a diagram of the energy density and power density of rechargeable chemical energy storage devices, and compares them with traditional lithium-ion batteries and capacitors;

Figure 3a is the first cycle charge and discharge curve of PTAm/NTCDA-PI battery at 0.5C rate, and Figure 3b is the cycle performance curve of PTAm/NTCDA-PI rechargeable chemical energy storage device at 5C rate;

Detailed ways

The principle of the rechargeable chemical energy storage device provided by the invention is different from traditional lithium ion batteries and sodium ion batteries. The principle is: the positive pole is an organic material capable of anion X ^- doping/dedoping; the negative pole is an organic or inorganic material capable of cationic M ⁺ intercalation/extraction; the electrolyte is an aqueous solution with a high MX salt concentration, non-aqueous Organic solution (preferably saturated solution) or molten salt system, etc. When charging, X ^- in the electrolyte is combined with the positive electrode, and M ⁺ is embedded in the negative electrode; when discharging, X ^- is separated from the positive electrode and enters the electrolyte, and M ⁺ comes out of the negative electrode and enters the electrolyte, releasing electrical energy at the same time.

The rechargeable chemical energy storage device of the present invention has a positive pole, a negative pole, a diaphragm and an electrolyte. The electrolyte is an aqueous solution with a high salt concentration, a non-aqueous organic solution or a molten salt system in which the mass fraction of the solute MX reaches 80-110% of the mass fraction in its saturated solution.

The positive electrode material described in the present invention is an organic material capable of anionic X ^- doping/dedoping, such as p-type organic polymers, free radical organics, non-conjugated organics, conductive polymers, or organic salts or inorganic porous Materials etc., preferred non-limiting examples are: poly-2,2,6,6-tetramethylpiperidinyl nitroxide radical-4-yl acrylamide (PTAm, code P _ca 1), poly-2, 2,6,6-Tetramethylpiperidinyl nitroxide-4-yl methyl methacrylate (PTMA, code P _ca 2), poly-1-oxo-2,2,6,6-tetra Methyl-piperidin-4-yl glycidyl ether (PTGE, code P _ca 3), poly-2,2,6,6-tetramethylpiperidinyl nitroxide-4-vinyl ether (PTVE , coded as P _ca 4), polyalkyne-2,2,6,6-tetramethyl-1-piperidinyl nitroxide-4-yl methyl p-benzoate (coded as P _ca 5), poly- Naphthalene[1,8-cd:4,5-c'd'][1,2]dithialo[dimethyl tetrathiofumarate] (code P _ca 6), polyethylene N-ethylene Carbazole (number P _ca 7), polytriphenylamine (number P _ca 8), polyaniline (PANI, number P _ca 9), aniline/o-nitroaniline copolymer, poly-2,2,5 , 5-tetramethyl-1-pyrrole nitroxide radical-3-yl propiolate methyl ester (code P _ca 10), polyyne-2,2,6,6-tetramethylpiperidine nitroxide radical Base-4-yl-4-ylglycidyl ether ether (numbered as P _ca 11), polypyrrole (PPy, numbered as P _ca 12), or compound, multi-stage polymerization, salt or group substitution of the above compounds etc., its molecular structural formula is shown in attached table 1. When making the positive electrode, you can also add conductive materials (such as graphite, carbon tubes, acetylene black, metal powder, conductive polymers or other organic functional molecules that improve electron or ion transport) and binders (such as polyvinylidene fluoride PVDF , polytetrafluoroethylene PTFE, cellulose CMC, water-soluble rubber SBR or other polymers, etc.), the above materials are mixed and evenly coated on stainless steel, Al foil, Ti foil, carbon felt, carbon cloth and other current collectors or pressed into sheets as positive electrode.

The negative electrode material of the present invention is an organic material or an inorganic material that can carry out cation M ⁺ intercalation/extraction (the preferred M ⁺ ion of the aqueous electrolyte is Na ⁺ ), such as n-type organic polymers, main chain type sulfur-containing organic polymers compounds, polysulfide polymers, organic carbonyl compounds, conductive polymers or embedded inorganic materials, etc. Preferred non-limiting examples are: 1,4,5,8-naphthalene tetracarboxylic anhydride-polyimide (NTCDA-PI, code P _an 1), poly-2,2'-dithioaniline (PDTDA, code P _an 2), poly α, α'-dithio-3-amino-o-xylene (PDTAn, number P _an 3), poly disulfide-2,5-dimercapto-1,3,4 -thiadiazole (PDMcT, number P _an 4), polyquinone (number P _an 5), poly-5-amino-1,4-naphthoquinone (number P _an 6), polyparaphenylene-3, 5-diamino-1,2,4-dithia (PPT, number P _an 7), poly-4,6-dihydro-1H-[1,2]dithio[4,5-c] Pyrrole (MPY, number P _an 8), polytrisulfide-2,5-dimercapto-1,3,4-thiadiazole (number P _an 9), poly-5,8-dihydro-1H, 4H-2,3,6,7-tetrasulfanthracene (code P _an 10), disodium terephthalate (Na ₂ C ₈ H ₄ O ₄ ) (code P _an 11), or a combination of the above compounds , multi-level polymerization, salt or group substitution, etc., the molecular structure formula is shown in Attached Table 1; or embedded inorganic materials such as graphite (number P _an 12), Li ₄ Ti ₅ O ₁₂ , NaTi ₂ (PO ₄ ) ₃ . When making the negative electrode, conductive materials (such as graphite, carbon tubes, acetylene black, metal powder, conductive polymers or other organic functional molecules that improve electron or ion transport) and binders (such as polyvinylidene fluoride PVDF, Polytetrafluoroethylene PTFE, cellulose CMC, water-soluble rubber SBR or other polymers), the above materials are mixed and evenly coated on stainless steel, Al foil, Cu foil, Ti foil, carbon felt, carbon cloth and other current collectors or pressed into sheets as the negative pole.

The electrolyte solution of the present invention can be selected from water system or non-aqueous organic system electrolyte according to different positive and negative electrode materials. Among them, the water-based electrolyte can be selected as non-limiting: NaNO ₃ , NaCl, Na ₂ SO ₄ , NaOH, NaBF ₄ , NaPF ₆ , NaClO ₄ , etc., where the mass fraction of the solute MX reaches 80-110% of the mass fraction in the saturated solution Aqueous solutions of one or more sodium salts. The non-aqueous organic electrolyte can be preferably non-limiting: NaBF ₄ , NaPF ₆ , NaClO ₄ , NaFSI, NaTFSI, LiBF ₄ , LiPF ₆ , LiTFSI with the mass fraction of the solute MX reaching 80-110% of the mass fraction in the saturated solution , LiFSI and other organic salts are dissolved in ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), tetrahydrofuran (THF), dimethoxy Diethylene glycol dimethyl ether (DME), diglyme (DG), diethylene glycol dimethyl ether (DGDME), triethylene glycol dimethyl ether (TGDME), tetraethylene glycol dimethyl ether ( TEGDME), 1,3-dioxolane (DOL), 4-methyl-1,3-dioxolane (4-MeDOL), γ-butyrolactone (γ-BL), methyl formate (MF), methyl acetate (MA), ethyl acetate (EA), methyl propionate (MP), ethyl propionate (EP), acetonitrile, propionitrile, malononitrile, 3-methoxypropionitrile A co-melt of one or more mixed solvents, or a molten salt system such as NaFSI/KFSI or LiFSI/KFSI.

Below in conjunction with specific embodiment, further illustrate the present invention. However, these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention.

Example 1

Grind the positive electrode material PTAm (P _an 1) with carbon tubes and binders at a ratio of 80%, 15%, and 5%, but not limited to this ratio, grind them evenly, coat them on a stainless steel mesh, and dry the pole pieces stand-by. The negative electrode material NTCDA-PI (P _an 1) is mixed with carbon tubes and binders according to the ratio of 80%, 15%, 5%, but not limited to this ratio, ground evenly, coated on the stainless steel mesh, and the pole piece is baked Dry and set aside. Using non-woven fabric as the diaphragm, 10M NaNO ₃ aqueous solution as the electrolyte, the positive and negative electrodes are assembled into a rechargeable chemical energy storage device, which is charged and discharged at 0.5C, 1C and 5C rates. Figure 2 shows the rechargeable chemical energy storage device 0.5 C rate charge-discharge curve in the first week and cycle performance at 5C rate (the capacity retention rate after 500 cycles is 95%).

Example 2

Following the method of electrode preparation in Example 1, carbon felt was used as the current collector, and positive electrode PTMA (P _ca 2) and negative electrode NTCDA-PI (P _an 1) pole pieces were prepared respectively, non-woven fabric was used as separator, and 6M NaCl aqueous solution was used as Electrolyte, assemble the positive and negative electrodes into a rechargeable chemical energy storage device, charge and discharge at 0.5C and 5C rates, see Table 1.

Example 3

Following the method of electrode preparation in Example 1, positive PTGE (P _ca 3) and negative NTCDA-PI (P _an 1) pole pieces were prepared respectively, using non-woven fabric as a diaphragm, and a saturated aqueous solution of NaPF ₆ as an electrolyte. The negative plate is assembled with a rechargeable chemical energy storage device, which is charged and discharged at a rate of 0.5C and 5C, as shown in Table 1.

Example 4

Following the method of electrode preparation in Example ₁ , positive electrode PTVE (P _ca 4) and negative electrode NTCDA-PI (P _an 1) pole pieces were prepared respectively, non-woven fabric was used as diaphragm, NaBF saturated aqueous solution was used as electrolyte, and positive electrode The negative plate is assembled with a rechargeable chemical energy storage device, which is charged and discharged at a rate of 0.5C and 5C, as shown in Table 1.

Example 5

Following the method of electrode preparation in Example 1, positive polytriphenylamine (P _ca 8) and negative NTCDA-PI (P _an 1) pole pieces were prepared respectively, using non-woven fabric as separator, and saturated aqueous solution of NaCl as electrolyte. The positive and negative plates are assembled with rechargeable chemical energy storage devices, which are charged and discharged at 0.5C and 5C rates, see Table 1.

Example 6

Follow the method for preparing the electrode in Example 1, using carbon cloth as the current collector, and prepare the positive polyacetylene-2,2,6,6-tetramethylpiperidine nitroxide radical-4-yl-4-ylglycidol respectively Ether-based ether (P _ca 11), negative NTCDA-PI (P _an 1) pole piece, using non-woven fabric as separator, NaBF ₄ saturated aqueous solution as electrolyte, the positive and negative pole pieces assembled rechargeable chemical energy storage device , charge and discharge at 0.5C and 5C rates, see Table 1.

Example 7

Following the method of electrode preparation in Example 1, positive electrode PTMA (P _ca 2) and negative electrode PDTDA (P _an 2) pole pieces were prepared respectively, using non-woven fabric as separator, _NaNO3 saturated aqueous solution as electrolyte, and positive and negative electrodes Chip-assembled rechargeable chemical energy storage devices, charged and discharged at 0.5C and 5C rates, see Table 1.

Example 8

Following the method of electrode preparation in Example 1, positive electrode PTGE (P _ca 3) and negative electrode PDTAn (P _an 3) pole pieces were prepared respectively, using non-woven cotton cloth as a diaphragm, and a saturated aqueous solution of NaPF ₆ as an electrolyte. Chip-assembled rechargeable chemical energy storage devices, charged and discharged at 0.5C and 5C rates, see Table 1.

Example 9

Following the method of electrode preparation in Example 1, positive electrode PTVE (P _ca 4) and negative electrode PDMcT (P _an 4) pole pieces were prepared respectively, using non-woven cotton cloth as separator, 10M NaNO ₃ aqueous solution as electrolyte, and positive and negative pole pieces Assemble rechargeable chemical energy storage devices, charge and discharge at 0.5C and 5C rates, see Table 1.

Example 10

Follow the method of electrode preparation in Example 1 to prepare positive polyacetylene-2,2,6,6-tetramethyl-1-piperidinyl nitroxide radical-4-yl methyl p-benzoate (P _ca 5) 1. Negative electrode polyquinone (P _an 5) pole piece, using non-woven cotton cloth as the diaphragm, NaBF ₄ saturated aqueous solution as the electrolyte, the positive and negative pole pieces are assembled into a rechargeable chemical energy storage device battery, charged and discharged at 0.5C and 5C rates , see Table 1.

Example 11

Following the method of electrode preparation in Example 1, the positive electrode poly-naphthalene [1,8-cd:4,5-c'd'] and [1,2] dithiacene [tetrathiofumaric acid di Methyl ester] (P _ca 6), negative electrode poly 5-amino-1,4-naphthoquinone (P _an 6) pole piece, use non-woven cotton cloth as separator, NaBF ₄ saturated aqueous solution as electrolyte, positive and negative pole piece Assemble rechargeable chemical energy storage devices, charge and discharge at 0.5C and 5C rates, see Table 1.

Example 12

Follow the method of electrode preparation in Example 1 to prepare positive poly N-vinyl carbazole (P _ca 7) and negative PPT (P _an 7) pole pieces respectively. Non-woven cotton cloth is used as separator, and saturated aqueous solution of NaBF ₄ is used as electrolyte , assemble the positive and negative electrodes into a rechargeable chemical energy storage device, charge and discharge at 0.5C and 5C rates, see Table 1.

Example 13

For example, following the method of electrode preparation in Example 1, positive polytriphenylamine (P _ca 8) and negative electrode MPY (P _an 8) pole pieces were prepared respectively, using non-woven cotton cloth as a separator, and a saturated aqueous solution of NaBF ₄ as an electrolyte. The positive and negative plates are assembled with rechargeable chemical energy storage devices, which are charged and discharged at 0.5C and 5C rates, see Table 1.

Example 14

Following the method of electrode preparation in Example 1, positive polyaniline (P _ca 9) and negative NTCDA-PI (P _an 1) pole pieces were prepared respectively, using non-woven cotton cloth as a diaphragm, and a saturated aqueous solution of _NaNO3 as an electrolyte. The positive and negative plates are assembled with rechargeable chemical energy storage devices, which are charged and discharged at 0.5C and 5C rates, see Table 1.

Example 15

Following the method for electrode preparation in Example 1, positive aniline/o-nitroaniline copolymers and negative NTCDA-PI (P _an 1) pole pieces were prepared respectively, using non-woven cotton as a diaphragm, and NaNO _The saturated aqueous solution was used as an electrolyte, Assemble the positive and negative electrodes into a rechargeable chemical energy storage device, charge and discharge at 0.5C and 5C rates, see Table 1.

Example 16

Follow the method of electrode preparation in Example 1 to prepare positive poly-2,2,5,5-tetramethyl-1-pyrrole nitroxide radical-3-yl propiolate methyl ester (P _ca 10), poly Trisulfide-2,5-dimercapto-1,3,4-thiadiazole (P _an 9) pole pieces, using non-woven cotton as a diaphragm, NaBF ₄ saturated aqueous solution as an electrolyte, the positive and negative pole pieces can be assembled Charge chemical energy storage devices, charge and discharge at 0.5C and 5C rates, see Table 1.

Example 17

Following the method of electrode preparation in Example 1, positive polypyrrole (P _ca 12), negative poly-5,8-dihydro-1H,4H-2,3,6,7-tetrathioanthracene (P _an 10 ) pole piece, using non-woven cotton cloth as the diaphragm, and the saturated aqueous solution of NaBF ₄ as the electrolyte, the positive and negative pole pieces are assembled into a rechargeable chemical energy storage device, and charged and discharged at 0.5C and 5C rates, see Table 1.

Example 18

Following the preparation method of the rechargeable chemical energy storage device in Examples 1-17, the positive electrode, negative electrode, and electrolyte can be combined arbitrarily, and charged and discharged at 0.5C and 5C rates, see Table 1.

Example 19

Following the method of electrode preparation in Example 1, using Al foil as the current collector, respectively prepare positive electrode PTAm (P _ca 1), negative electrode disodium terephthalate (P _an 11) pole pieces, use glass fiber as separator, NaBF ₄ The saturated solution of /PC is used as the electrolyte, and the positive and negative electrodes are assembled into a rechargeable chemical energy storage device, which is charged and discharged at a rate of 0.5C and 5C, as shown in Table 2.

Example 20

Following the method for preparing the electrode in Example 1, using Ti foil as the current collector, the positive electrode poly-naphthalene[1,8-cd:4,5-c'd'][1,2]dithiacene[ Dimethyl tetrathiofumarate] (P _ca 6), negative electrode disodium terephthalate (P _an 11) pole piece, using glass fiber as separator, NaPF ₆ /TEGDME saturated solution as electrolyte, positive The negative plate is assembled with a rechargeable chemical energy storage device, which is charged and discharged at a rate of 0.5C and 5C, see Table 2.

Example 21

Following the method of electrode preparation in Example 1, using stainless steel as the current collector, respectively prepare positive electrode PTGE (P _ca 3) and negative electrode disodium terephthalate (P _an 11) pole pieces, using glass fiber as the diaphragm, NaTFSI/γ The saturated solution of -BL is used as the electrolyte, and the positive and negative electrodes are assembled into a rechargeable chemical energy storage device, which is charged and discharged at a rate of 0.5C and 5C, as shown in Table 2.

Example 22

Following the method of electrode preparation in Example 1, using Al foil as the current collector, respectively prepare positive poly N-vinyl carbazole (P _ca 7) and negative disodium terephthalate (P _an 11) pole pieces, using glass The fiber is used as a separator, the saturated solution of NaBF ₄ /EA is used as an electrolyte, and the positive and negative electrodes are assembled into a rechargeable chemical energy storage device, which is charged and discharged at a rate of 0.5C and 5C, as shown in Table 2.

Example 23

Following the method of electrode preparation in Example 1, using Al foil as a current collector, respectively prepare positive pole polytriphenylamine (P _ca 8) and negative pole disodium terephthalate (P _an 11) pole pieces, using glass fiber as a diaphragm, The saturated solution of NaBF ₄ /PC is used as the electrolyte, and the positive and negative electrodes are assembled into a rechargeable chemical energy storage device, which is charged and discharged at a rate of 0.5C and 5C, see Table 2.

Example 24

Following the method of electrode preparation in Example 1, positive electrode PTAm (P _ca 1) (using Al foil as current collector) and negative electrode graphite (P _an 12) pole piece (using Cu foil as current collector) were prepared respectively, using glass fiber as The diaphragm, the saturated solution of LiTFSI/PC is used as the electrolyte, and the positive and negative electrodes are assembled into a rechargeable chemical energy storage device, which is charged and discharged at a rate of 0.5C and 5C, as shown in Table 2.

Example 25

Following the method of electrode preparation in Example 1, positive electrode PTGE (P _ca 3) (using Ti foil as current collector) and negative electrode graphite (P _an 12) pole piece (using Cu foil as current collector) were prepared respectively, using glass fiber as The diaphragm, the saturated solution of LiFSI/PC is used as the electrolyte, and the positive and negative electrodes are assembled into a rechargeable chemical energy storage device, which is charged and discharged at a rate of 0.5C and 5C, as shown in Table 2.

Example 26

Following the method of electrode preparation in Example 1, the positive electrode poly-naphthalene [1,8-cd:4,5-c'd'] and [1,2] dithiacene [tetrathiofumaric acid di Methyl ester] (P _ca 6) (using Al foil as the current collector), negative electrode graphite (P _an 12) pole piece (using Cu foil as the current collector), using glass fiber as the diaphragm, and the saturated solution of LiPF ₆ /PC as the electrolytic Assembled the positive and negative plates into a rechargeable chemical energy storage device, charged and discharged at 0.5C and 5C rates, see Table 2.

Example 27

Following the method for preparing the positive electrode of the rechargeable chemical energy storage device in Example 1-18, the negative electrode graphite (P _an 12) pole piece (using Cu foil as the current collector), using glass fiber as the separator, and the saturated solution of LiBF ₄ /PC as the Electrolyte, assemble the positive and negative electrodes into a rechargeable chemical energy storage device, charge and discharge at 0.5C and 5C rates, see Table 2.

Example 28

Following the method of electrode preparation in Example 1, positive pole PTAm (P _ca 1), negative pole NTCDA-PI (P _an 1) pole pieces were prepared respectively, using non-woven fabric as diaphragm, 10M NaNO ₃ and 1M KNO ₃ (as supporting electrolyte ) aqueous solution as the electrolyte, the positive and negative electrodes were assembled into a rechargeable chemical energy storage device, and charged and discharged at 0.5C and 5C rates, see Table 1.

Example 29

Following the method of electrode preparation in Examples 1-18, using non-woven fabric as separator, 10M NaNO ₃ and 0.5M KNO ₃ (as supporting electrolyte) in aqueous solution as electrolyte, the positive and negative electrodes are assembled into a rechargeable chemical energy storage device , Charge and discharge at 0.5C and 5C rates, see Table 1.

Example 30

The positive electrode material PTAm (P _an 1) is mixed with carbon tubes, binders and NaNO ₃ according to the ratio of 75%, 15%, 5%, 5%, but not limited to this ratio, ground evenly, and coated on the stainless steel mesh , and the pole pieces are dried for later use. The negative electrode material NTCDA-PI (P _an 1) is mixed with carbon tubes and binders according to the ratio of 80%, 15%, 5%, and 10%, but not limited to this ratio, ground evenly, and coated on the stainless steel mesh, The pole piece is ready to use after drying. Using non-woven fabric as the diaphragm, 10M NaNO ₃ aqueous solution as the electrolyte, the positive and negative electrodes were assembled into a rechargeable chemical energy storage device, and charged and discharged at 0.5C and 5C rates, see Table 1.

Example 31

Grind the positive electrode material PTMA (P _ca 2) with carbon tubes and binders at a ratio of 80%, 15%, and 5%, but not limited to this ratio, grind them evenly, coat them on the stainless steel mesh, and dry the pole pieces stand-by. Negative electrode material NTCDA-PI (P _an 1) and carbon tubes, binder and NaNO ₃ according to the ratio of 75%, 15%, 5%, 5%, but not limited to this ratio, grinding evenly, coating on Stainless steel mesh, pole pieces are dried for later use. Using non-woven fabric as the diaphragm, 10M NaNO ₃ aqueous solution as the electrolyte, the positive and negative electrodes were assembled into a rechargeable chemical energy storage device, and charged and discharged at 0.5C and 5C rates, see Table 1.

Example 32

The positive electrode material PTGE (P _ca 3) is mixed with carbon tubes, binders and NaPF ₆ according to the ratio of 75%, 15%, 5%, 5%, but not limited to this ratio, ground evenly, and coated on the stainless steel mesh , and the pole pieces are dried for later use. Negative electrode material disodium terephthalate (P _an 11) and carbon tube, binder according to the ratio of 80%, 15%, 5%, but not limited to this ratio, grind evenly, coat on the stainless steel mesh, The pole piece is ready to use after drying. Glass fiber is used as a separator, a saturated solution of NaPF ₆ /PC is used as an electrolyte, and the positive and negative electrodes are assembled into a rechargeable chemical energy storage device. Charge and discharge at 0.5C and 5C rates, see Table 2.

Example 33

Following the method of electrode preparation in Example 33, prepare positive electrode PTVE (P _ca 4) respectively, and carbon tubes and binders according to the ratio of 80%, 15%, and 5%, but not limited to this ratio, and the grinding is uniform. Coated on the stainless steel mesh, and the pole pieces are dried for later use. Negative electrode material disodium terephthalate (P _an 11) and carbon tubes, binder and NaPF ₆ according to the ratio of 75%, 15%, 5%, 5%, but not limited to this ratio, grind evenly, Coated on the stainless steel mesh, and the pole pieces are dried for later use. Glass fiber is used as a separator, a saturated solution of NaPF ₆ /PC is used as an electrolyte, and the positive and negative electrodes are assembled into a rechargeable chemical energy storage device. Charge and discharge at 0.5C and 5C rates, see Table 2.

Example 34

The positive electrode material PTGE (P _ca 3) is mixed with carbon tubes, binder and LiPF ₆ according to the ratio of 75%, 15%, 5%, 5%, but not limited to this ratio, ground evenly, and coated on the stainless steel mesh , and the pole pieces are dried for later use. The negative electrode material graphite (P _an 12) is mixed with carbon tubes and binders at a ratio of 80%, 15%, and 5%, but not limited to this ratio, ground evenly, and coated on Cu foil, and the pole pieces are dried stand-by. Glass fiber is used as a separator, and a saturated solution of LiPF ₆ /PC is used as an electrolyte, and the positive and negative electrodes are assembled into a rechargeable chemical energy storage device. Charge and discharge at 0.5C and 5C rates, see Table 2.

Example 35

The anode material polytriphenylamine (P _ca 8) is mixed with carbon tubes and binders according to the ratio of 80%, 15%, 5%, but not limited to this ratio, ground evenly, and coated on the Al foil. The slices are dried for later use. The anode material graphite (P _an 12) is mixed with carbon tubes, binder and LiPF ₆ according to the ratio of 75%, 15%, 5%, 5%, but not limited to this ratio, grind evenly, and coat on Cu foil On, the pole pieces are dried and set aside. Glass fiber is used as a separator, and a saturated solution of LiPF ₆ /PC is used as an electrolyte, and the positive and negative electrodes are assembled into a rechargeable chemical energy storage device. Charge and discharge at 0.5C and 5C rates, see Table 2.

Table 1: Performance of rechargeable chemical energy storage devices in Examples 1-18, 28-31 (aqueous electrolyte)

Table 2: Secondary battery performance in Examples 19-27, 32-35 (non-aqueous organic electrolyte)

Attached Table 1: Organic Molecular Structural Formula

Claims (14)

1. A rechargeable chemical energy storage device, comprising: positive pole, negative pole, separator and electrolyte, characterized in that the positive pole material is an organic material that can carry out anion X ^- doping/dedoping; the negative pole material is an organic material that can carry out cation M ⁺ Intercalated/extracted organic or inorganic materials; the electrolyte is an aqueous solution with a high salt concentration, a non-aqueous organic solution or a molten salt system in which the mass fraction of the solute MX reaches 80-110% of the mass fraction in its saturated solution. 2. The rechargeable chemical energy storage device according to claim 1, characterized in that, the state and potential of the solute salt anion and cation in the electrolyte solution with high salt concentration are combined with the positive and negative electrodes respectively and the difference in potential is realized through the gain and loss of electrons charging and discharging. The anions and cations of the solute salt in the electrolyte participate in the reversible combination/decombination process of the positive and negative electrodes respectively, realizing reversible charge and discharge and storage of electric energy. Its charging and discharging characteristics are different from traditional capacitors and lithium-ion batteries. During charging and discharging, the differential dE/dQ value of voltage E and electric quantity Q may not be constant or equal to zero. 3. According to the rechargeable chemical energy storage device described in claim 1-2, it is characterized in that its anode material adopts: an organic material capable of anion X ^- doping/dedoping, such as p-type organic polymer, free Based organics, non-conjugated organics, conductive polymers, organic salts, etc., or composites, multi-stage polymerizations, salts or group substitutions of the above compounds. 4. The rechargeable chemical energy storage device according to the requirements of claims 1-2, characterized in that, its negative electrode material adopts: an organic or inorganic material capable of intercalating/extracting cation M ⁺ , such as n-type organic polymer, main chain Type sulfur-containing organic polymers, polysulfide polymers, organic carbonyl compounds, conductive polymers, carbon-based materials, or composites, multi-stage polymerizations, salts or group substitutions of the above compounds; or embedded inorganic materials. 5. The rechargeable chemical energy storage device according to claim 3, wherein the positive electrode material is: poly-2,2,6,6-tetramethylpiperidine nitroxide-4-yl Acrylamide (P _ca 1), poly-2,2,6,6-tetramethylpiperidinyl nitroxide-4-yl methyl methacrylate (P _ca 2), poly-1-oxo-2 ,2,6,6-Tetramethyl-piperidin-4-yl glycidyl ether (P _ca 3), poly-2,2,6,6-tetramethylpiperidinyl nitroxide-4-ethylene Base ether (P _ca 4), polyalkyne-2,2,6,6-tetramethyl-1-piperidinyl nitroxide-4-yl methyl p-benzoate (P _ca 5), poly-naphthalene[ 1,8-cd:4,5-c'd'][1,2]dithialo[dimethyl tetrathiofumarate] (P _ca 6), poly N-vinylcarbazole ( P _ca 7), polytriphenylamine (P _ca 8), polyaniline (P _ca 9), aniline/o-nitroaniline copolymer, poly-2,2,5,5-tetramethyl-1-pyrrole nitroxide Radical-3-ylpropiolic acid methyl ester (P _ca 10), polyalkyne-2,2,6,6-tetramethylpiperidinyl nitroxide radical-4-yl-4-ylglycidyl ether group Diethyl ether P _ca 11), or polypyrrole (P _ca 12), or compound, multi-stage polymerization, salt or group substitution of the above compounds. 6. according to the described rechargeable chemical energy storage device of claim 4, it is characterized in that, described negative electrode material is: 1,4,5,8-naphthalene tetracarboxylic anhydride-polyimide (P _an 1), Poly-2,2'-dithioaniline (P _an 2), poly α,α'-dithio-3-amino-o-xylene (P _an 3), poly disulfide-2,5-dimercapto -1,3,4-thiadiazole (P _an 4), polyquinone (P _an 5), poly-5-amino-1,4-naphthoquinone (P _an 6), poly-p-phenylene-3,5- Diamino-1,2,4-dithia (P _an 7), poly-4,6-dihydro-1H-[1,2]dithio[4,5-c]pyrrole (P _an 8) , polytrisulfide-2,5-dimercapto-1,3,4-thiadiazole (P _an 9), poly-5,8-dihydro-1H,4H-2,3,6,7-tetrasulfide Anthracene (P _an 10), or disodium terephthalate (P _an 11), or compound, multi-stage polymerization, salt or group substitution of the above compounds. The negative electrode can also be other embedded inorganic materials such as graphite (P _an 12), Li ₄ Ti ₅ O ₁₂ , NaTi ₂ (PO ₄ ) ₃ . 7. According to the rechargeable chemical energy storage device required by rights 1-6, it is characterized in that conductive materials and binders can also be added when making positive and negative pole pieces, and the above materials are mixed and evenly coated on stainless steel, Al foil, Cu foil, Ti foil, carbon felt, carbon cloth current collector or pressed into sheets are used as positive and negative electrodes. 8. According to the rechargeable chemical energy storage device required by rights 1-7, it is characterized in that the electrolyte is an aqueous solution with a high MX salt concentration, a non-aqueous organic solution or a molten salt system, etc., wherein the M ⁺ ion is Na ⁺ or Li ⁺ ions. The definition of high MX salt concentration is that the mass fraction of solute MX reaches 80-110% of the mass fraction in its saturated solution. 9. The rechargeable chemical energy storage device according to the requirements of claims 1-8, characterized in that the aqueous electrolyte is: NaNO ₃ whose mass fraction of the solute MX reaches 80-110% of the mass fraction in its saturated solution, An aqueous solution of one or more sodium salts of NaCl, Na ₂ SO ₄ , NaOH, NaBF ₄ , NaPF ₆ , NaClO ₄ , preferably a saturated solution. 10. The rechargeable chemical energy storage device according to the requirements of claims 1-8, characterized in that, the non-aqueous organic electrolyte is: the mass fraction of the solute MX reaches 80-110% of the mass fraction in its saturated solution One or more organic salts of NaBF ₄ , NaPF ₆ , NaClO ₄ , NaFSI, NaTFSI, LiBF ₄ , LiPF ₆ , LiTFSI, LiFSI are dissolved in ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate ( DMC), diethyl carbonate (DEC), tetrahydrofuran (THF), dimethoxyethane (DME), diglyme (DG), diethylene glycol dimethyl ether (DGDME), tris Ethylene glycol dimethyl ether (TGDME), tetraethylene glycol dimethyl ether (TEGDME), 1,3-dioxolane (DOL), 4-methyl-1,3-dioxolane ( 4-MeDOL), γ-butyrolactone (γ-BL), methyl formate (MF), methyl acetate (MA), ethyl acetate (EA), methyl propionate (MP), ethyl propionate ( EP), acetonitrile, propionitrile, malononitrile, 3-methoxypropionitrile or one or more mixed solvents, preferably a saturated solution. 11. The rechargeable chemical energy storage device according to claim 1-8, wherein the molten salt electrolyte system is a eutectic of NaFSI/KFSI or LiFSI/KFSI. 12. The rechargeable chemical energy storage device according to claims 1-11, characterized in that, the aqueous or organic non-aqueous electrolyte can also be added with other supporting electrolytes, so that the rechargeable chemical energy storage device described in the present invention The electrolyte in the charged final state of the device still has a high conductivity. Specifically, such as: electrolyte salt containing K ⁺ and N(C ₄ H ₉ ) ₄ ⁺ . The definition of supporting electrolyte is: at least one of the anion and cation of the solute salt in the electrolyte does not participate in the combination/decombination process with the positive and negative electrodes, and its concentration range is 0.01M~1M. 13. The rechargeable chemical energy storage device according to the requirements of claims 1-12, characterized in that electrolyte salt can also be added when making the positive and negative pole pieces, and the rechargeable chemical energy storage device is in the final state of charging, and the electrolyte The anion and cation are combined with the positive and negative electrodes, the conductivity of the electrolyte decreases, and the electrolyte salt in the positive and negative plates dissolves into the electrolyte to reduce the electric field polarization inside the battery caused by the decrease in the conductivity of the electrolyte at the end of charging. 14. The rechargeable chemical energy storage device according to claims 1-13 can be applied to large-scale energy storage such as solar power generation, wind power generation, distributed power stations, smart buildings, and smart grids, as well as data centers, communication base stations, industrial energy storage, national Security and other large-scale energy storage fields are not limited to this.

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