CN110835104A - Preparation method of nitrogen-doped carbon nanosheet, negative electrode active material and dual-ion battery - Google Patents
Preparation method of nitrogen-doped carbon nanosheet, negative electrode active material and dual-ion battery Download PDFInfo
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Abstract
The invention belongs to the technical field of battery materials, and particularly relates to a preparation method of nitrogen-doped carbon nanosheets, a negative electrode active material and a dual-ion battery. The preparation method of the nitrogen-doped carbon nanosheet comprises the following steps: providing an organic acid and an organic primary amine, wherein the organic acid contains a carboxyl group; dissolving the organic acid and the organic primary amine in a solvent for heating treatment, and then drying to obtain a precursor; and calcining and carbonizing the precursor to obtain the nitrogen-doped carbon nanosheet. The preparation method is simple in process and low in cost, the finally obtained nitrogen-doped carbon nanosheet material is stable in structure, has the characteristics of high specific capacity and stable voltage when being used as a battery cathode active material, and shows excellent cycling stability, so that the selection range of the battery cathode active material is widened, and the preparation method has a good application prospect in the field of batteries.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a preparation method of nitrogen-doped carbon nanosheets, a negative electrode active material and a dual-ion battery.
Background
Lithium Ion Batteries (LIBs) are secondary batteries that can be repeatedly charged and discharged and used many times, and are widely used in various industries due to their high energy density, high operating voltage, environmental friendliness, light weight, and long cycle life, but they also face the disadvantages of limited lithium resource storage. Commercial lithium ion batteries are generally based on transition metal oxides (LiCoO)2、LiMn2O4、LiNiCoMnO2) Or polyanionic metal oxides (LiFePO)4) The lithium ion battery is a positive active material, graphite or carbon is used as a negative active material, ester electrolyte or polymer gel is used as electrolyte, the price of the positive active material containing transition metal elements such as Ni, Co, Mn and the like is increasingly higher, and the waste battery has great harm to the environment. The search for novel, cheap and environment-friendly energy storage devices is not slow. Compared with lithium element, sodium and potassium elements have higher natural abundance and low price, and have the prospect of large-scale application. Potassium and lithium elements belong to the same group and have similar chemical properties, and the voltage window of potassium ion batteries (KIBs) is similar to that of LIBs, so that the energy density is comparable to that of common commercial LIBs.
Among the representative components (including positive electrode, negative electrode, electrolyte, separator, and the like) constituting the secondary battery, the negative electrode generally includes a negative electrode current collector and a negative electrode active material. Among them, the negative active material is critical to whether the secondary battery can realize high capacity and high cycle performance. For example, KIBs generally use graphite-based materials as negative electrode active materials, and the large potassium ion radius results in rapid expansion of graphite layer spacing due to KCx compounds formed, which easily causes collapse of carbon material structure during expansion and contraction, resulting in unsatisfactory battery cycle performance. In order to solve the problems, researchers regulate and control the carbon material by element doping so as to improve the cycle performance and rate performance of the carbon material; however, the existing nitrogen-carbon material preparation method is complex, is difficult to produce in a large scale, and causes high material cost.
Therefore, the prior art is in need of improvement.
Disclosure of Invention
The invention aims to provide a preparation method of nitrogen-doped carbon nanosheets, a negative electrode active material and a dual-ion battery, and aims to solve the technical problems that the existing nitrogen-doped carbon material is not ideal in electrochemical performance and complex in preparation process.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of nitrogen-doped carbon nanosheets, which comprises the following steps:
providing an organic acid and an organic primary amine, wherein the organic acid contains a carboxyl group;
dissolving the organic acid and the organic primary amine in a solvent for heating treatment, and then drying to obtain a precursor;
and calcining and carbonizing the precursor to obtain the nitrogen-doped carbon nanosheet.
On the other hand, the invention provides a negative active material, which is the nitrogen-doped carbon nanosheet obtained by the preparation method.
The invention also provides a negative electrode, which comprises a negative electrode current collector and a negative electrode active layer combined on the surface of the negative electrode current collector, wherein the negative electrode active layer contains a negative electrode active material, a conductive agent and a binder; the negative active material comprises the nitrogen-doped carbon nanosheet obtained by the preparation method.
The invention finally provides a bi-ion battery, which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the diaphragm and the electrolyte are positioned between the positive electrode and the negative electrode, and the negative electrode is the negative electrode.
The preparation method of the nitrogen-doped carbon nanosheet provided by the invention takes organic acid containing carboxyl and organic primary amine as raw materials, firstly, the organic acid containing carboxyl and the organic primary amine are dissolved in a solvent for heating treatment, so that the carboxyl of the organic acid and the amino of the organic primary amine are subjected to condensation reaction, then, the solvent is dried and removed to obtain a precursor solid for calcination, and the precursor is calcined and carbonized to obtain the high-nitrogen-doped carbon nanosheet; the preparation method is simple in process and low in cost, the finally obtained nitrogen-doped carbon nanosheet material is stable in structure, has the characteristics of high specific capacity and stable voltage when being used as a battery cathode active material, and shows excellent cycling stability, so that the selection range of the battery cathode active material is widened, and the preparation method has a good application prospect in the field of batteries.
The negative active material provided by the invention is the nitrogen-doped carbon nanosheet obtained by the special preparation method, so that the negative active material has the characteristics of high specific capacity and stable voltage, shows excellent cycling stability and has a good application prospect in the field of batteries.
According to the battery cathode and the dual-ion battery, the nitrogen-doped carbon nanosheet obtained by the preparation method is used as the cathode active material, and the cathode active material obtained by the special preparation method has stable structure and excellent electrochemical performance, so that the dual-ion battery has excellent cycling stability.
Drawings
Fig. 1 is a schematic flow chart of a method for preparing nitrogen-doped carbon nanosheets according to the present invention;
fig. 2 is a schematic structural diagram of a bi-ion battery according to the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In one aspect, an embodiment of the present invention provides a method for preparing a nitrogen-doped carbon nanosheet, as shown in fig. 1, the method includes the following steps:
s01: providing an organic acid and an organic primary amine, wherein the organic acid contains a carboxyl group;
s02: dissolving the organic acid and the organic primary amine in a solvent for heating treatment, and then drying to obtain a precursor;
s03: and calcining and carbonizing the precursor to obtain the nitrogen-doped carbon nanosheet.
According to the preparation method of the nitrogen-doped carbon nanosheet, provided by the embodiment of the invention, the organic acid containing carboxyl and the organic primary amine are used as raw materials, the organic acid containing carboxyl and the organic primary amine are dissolved in a solvent to be heated, so that the carboxyl of the organic acid and the amino of the organic primary amine are subjected to condensation reaction, then a precursor solid for calcination is obtained after the solvent is dried, and the precursor is calcined and carbonized to obtain the high-nitrogen-doped carbon nanosheet; the preparation method is simple in process and low in cost, the finally obtained nitrogen-doped carbon nanosheet material is stable in structure, has the characteristics of high specific capacity and stable voltage when being used as a battery cathode active material, and shows excellent cycling stability, so that the selection range of the battery cathode active material is widened, and the preparation method has a good application prospect in the field of batteries.
In step S01, the carboxyl group-containing organic acid and the organic primary amine are raw materials for preparing the nitrogen-doped carbon nanosheet. In one embodiment, the organic acid comprises a hydroxy acid, specifically, at least one of citric acid, glycolic acid, tartaric acid, malic acid, and lactic acid; and the organic primary amine comprises at least one of acetamide, propionamide and urea; the organic acid contains abundant carboxyl and hydroxyl, and can better react with amino of organic primary amine to form a precursor. In a preferred embodiment, the organic acid is citric acid and the primary organic amine is urea (i.e., carbamide).
In the step S02, the organic acid and the organic primary amine are dissolved in the solvent and heated in a water bath; the temperature of the heating treatment is 40-85 ℃, and the time of the heating treatment is 3-7 h; the above temperature and time ranges are such that the condensation reaction of the organic acid and the organic primary amine proceeds better. In a preferred embodiment, the temperature of the water bath heating is 75 ℃, and the time of the water bath heating is 5 h. After heating in water bath, drying at the temperature of 70-120 ℃ for 6-13 h; preferably at 100 ℃ to reduce agglomeration caused by too high temperature, and preferably for 12h, under the above-mentioned drying temperature and time conditions, the calcined precursor can be obtained.
The solvent for dissolving the organic acid and the organic primary amine is a mixed solvent of alcohol and water, and the water in the mixed solvent can reduce the evaporation of the alcohol at higher temperature, thereby being beneficial to better reaction of the organic acid and the organic primary amine. Wherein the alcohol comprises at least one of methanol, ethanol, ethylene glycol and propanol, preferably ethanol. The volume ratio of alcohol to water in the solvent is (1-10):1, and in one embodiment, the volume ratio of ethanol to water is preferably 3: 1.
in one embodiment, the mass ratio of the organic acid to the organic primary amine is 1 (5-15). In order to ensure that the precursor product carries more nitrogen elements, an excessive treatment mode of organic primary amine is adopted. In a particular embodiment, the citric acid and urea are mixed in a mass ratio of 1:5 to 15, preferably 1: 10. The excess urea is effective in preventing the self-polymerization phenomenon of citric acid at higher temperatures.
In the above step S03, the calcination carbonization process includes: the temperature is raised to 400 ℃ for 250-. The calcination carbonization is a two-step heating process, specifically, the first heat preservation is performed at the temperature of 250-400 ℃ to obtain a pre-carbonization process, and then the temperature is increased to the temperature of 550-750 ℃ to obtain a second heat preservation to obtain the complete carbonization. Organic acid and organic primary amine are dissolved in a solvent and are sequentially heated and dried, the organic acid and the organic primary amine are polymerized to form a precursor, and because the organic primary amine such as urea is excessive, the preliminary carbonization is carried out at a lower temperature (250-400 ℃), so that the defect that the corresponding carbon nitride product is generated due to too small amount of carbonized products caused by severe urea decomposition can be prevented; in the embodiment of the method, the temperature is firstly raised to 250-400 ℃ for preliminary carbonization, and then raised to 550-750 ℃ for complete carbonization, so that the nitrogen-doped carbon nanosheet material with high yield and excellent capacity and cycle life in electrochemistry can be prepared.
Wherein the first heat preservation time is 2-5 h; the second heat preservation time is 3-6 h; the heating rate is 2-5 ℃/mim in the calcining carbonization process. In order to save cost and ensure the performance of the nitrogen-doped carbon material, the heat preservation time is more than 2 hours but generally not more than 6 hours, the temperature rise rate is determined according to the initial carbonization temperature and time of the first step, and the temperature rise rate is 2.5 ℃/mim if the initial carbonization temperature of the first step is 350 ℃ and the time is 2 hours. In a preferred embodiment, the two-step heating calcination carbonization process comprises: firstly, heating to 350 ℃ at a heating rate of 2 ℃/mim, and preserving heat for 2 hours; then the temperature is raised to 650 ℃ at the temperature raising speed of 5 ℃/mim, and the temperature is kept for 4 h.
In one embodiment, the calcination carbonization is performed in an inert atmosphere.
In a specific embodiment, the method for preparing the nitrogen-doped carbon nanosheet includes the following steps:
(1) pretreatment: taking 200ml of water: pouring the mixed solution of ethanol (the volume ratio is 1:3) into a beaker, uniformly mixing, weighing 1g of citric acid and 5-15g of urea, and adding into the mixed solution.
(2) Heating in water bath: adding a magnetic stirring bar into the solution dissolved in the step (1) and stirring until the solution is clear. Subsequently, the mixture was heated in a water bath at 75 ℃ for 5 hours, and dried in an oven at 100 ℃ for 12 hours after the reaction to obtain a precursor.
(3) And putting the precursor into a corundum porcelain boat, and covering. Placing the mixture into a tube furnace, sealing the furnace, introducing 30 mm of argon, removing air in the tube, and heating the tube furnace in two steps to obtain a target product: firstly, heating to 350 ℃, and preserving heat for 2 hours, wherein the heating rate is 2 ℃/mim; then the temperature is raised to 650 ℃, the temperature is preserved for 4 hours, and the temperature raising speed is 5 ℃/mim. And (3) protecting the whole process with argon, wherein the gas flow is 80-140ccm, and obtaining the final product of the nitrogen-doped carbon nanosheet with high nitrogen content.
The high-nitrogen-doped carbon nanosheet material prepared by the embodiment of the invention can be used as a negative electrode active material in lithium ion batteries, sodium ion batteries, potassium ion batteries, calcium ion batteries, magnesium ion batteries and zinc ion batteries.
On the other hand, the embodiment of the invention also provides a negative electrode active material, wherein the negative electrode active material is the nitrogen-doped carbon nanosheet obtained by the preparation method of the embodiment of the invention. The negative active material provided by the embodiment of the invention is the nitrogen-doped carbon nanosheet obtained by the special preparation method of the embodiment of the invention, so that the negative active material has the characteristics of high specific capacity and stable voltage, shows excellent cycling stability and has a good application prospect in the field of batteries.
In yet another aspect, embodiments of the present invention further provide a negative electrode, including a negative electrode current collector and a negative electrode active layer bonded to a surface of the negative electrode current collector, where the negative electrode active layer includes a negative electrode active material, a conductive agent, and a binder; the negative electrode active material comprises the nitrogen-doped carbon nanosheet obtained by the preparation method provided by the embodiment of the invention.
Finally, the embodiment of the invention also provides a dual-ion battery, which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the diaphragm and the electrolyte are positioned between the positive electrode and the negative electrode, and the negative electrode is the negative electrode in the embodiment of the invention; namely, the negative electrode in the dual-ion battery comprises a negative electrode current collector and a negative electrode active layer combined on the surface of the negative electrode current collector, wherein the negative electrode active layer contains a negative electrode active material, a conductive agent and a binder; the negative electrode active material comprises the nitrogen-doped carbon nanosheet obtained by the preparation method provided by the embodiment of the invention.
According to the dual-ion battery provided by the embodiment of the invention, the nitrogen-doped carbon nanosheet obtained by the preparation method of the embodiment of the invention is used as the negative electrode active material, the negative electrode active material obtained by the specific preparation method has stable structure and excellent electrochemical performance, and the high-nitrogen-doped carbon nanosheet can be mixed with graphite materials (such as natural graphite, expanded graphite, artificial graphite and the like, but not limited to graphite materials) to be used as the negative electrode nano active material for forming batteries of lithium, sodium, potassium, calcium, magnesium, zinc and the like, so that the dual-ion battery has excellent cycle stability.
Specifically, the dual ion battery includes any one of a lithium ion battery, a sodium ion battery, a potassium ion battery, a calcium ion battery, a magnesium ion battery, and a zinc ion battery. Specifically, the double-ion battery is a potassium-ion battery, wherein the negative electrode active layer comprises a material capable of allowing potassium ions to be freely inserted and extracted, and the positive electrode active layer comprises a material capable of allowing anions composing potassium salt to be freely adsorbed and extracted. The nitrogen-doped carbon nanosheet is used as a negative active material, and can overcome the defects of unstable structure, poor circulation stability, more side reactions between the material and electrolyte and low ionic and electronic conductivity of the negative active material of the potassium ion secondary battery.
In the bi-ion battery, a negative electrode comprises a negative electrode current collector and a negative electrode active layer combined on the surface of the negative electrode current collector, wherein the negative electrode active layer contains a negative electrode active material, a conductive agent and a binder; the negative electrode active material comprises the nitrogen-doped carbon nanosheet obtained by the preparation method provided by the embodiment of the invention. The positive electrode comprises a positive electrode current collector and a positive electrode active layer combined on the surface of the positive electrode current collector, and the positive electrode active layer contains a positive electrode active material, a conductive agent and a binder; the positive electrode active material comprises one or more of carbon materials, sulfides, nitrides and oxides with a layered structure. The carbon material is selected from one or more of activated carbon, mesocarbon microbeads graphite, natural graphite, expanded graphite, glassy carbon, carbon-carbon composite materials, carbon fibers, hard carbon, porous carbon, highly-oriented graphite, carbon black, carbon nanotubes and graphene; the sulfide is selected from one or more of molybdenum disulfide, tungsten disulfide, vanadium disulfide, titanium disulfide, iron disulfide, ferrous sulfide, nickel sulfide, zinc sulfide, cobalt sulfide and manganese sulfide; the nitride is selected from one or more of hexagonal boron nitride and carbon-doped hexagonal boron nitride; the oxide is selected from one or more of molybdenum trioxide, tungsten trioxide, vanadium pentoxide, vanadium dioxide, titanium dioxide, zinc oxide, copper oxide, nickel oxide and manganese oxide or a compound thereof. The positive electrode active material may further include one or more of materials having a layered structure such as a carbon material, prussian blue and the like, a phosphorus-based compound, and the like. Preferably, the carbon material is preferably a graphite-based carbon material.
In the negative active layer of the negative electrode, the content of the negative active material may be 60 to 90 wt.%, the content of the conductive agent is 5 to 30 wt.%, and the content of the binder is 5 to 10 wt.%. In one embodiment, the negative active material may be highly nitrogen-doped carbon nanosheets mixed with acetylene black, and the content of the highly nitrogen-doped carbon nanosheets is 50-99 wt% of the total weight of the negative active material. The conductive agent comprises one or more of conductive carbon black, conductive carbon spheres, conductive graphite, carbon nanotubes, conductive carbon fibers, graphene and reduced graphene oxide. The binder comprises one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, SBR rubber and polyolefin.
In the positive electrode active layer of the positive electrode, the positive electrode active material may be contained in an amount of 60 to 90 wt.%, preferably 80 wt.%, the conductive agent may be contained in an amount of 5 to 30 wt.%, preferably 10%, and the binder may be contained in an amount of 5 to 10 wt.%, preferably 10%. Meanwhile, the conductive agent and the binder are not particularly limited and may be those commonly used in the art. The conductive agent is one or more of conductive carbon black, conductive carbon spheres, conductive graphite, carbon nanotubes, conductive carbon fibers, graphene and reduced graphene oxide. The binder is one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, SBR rubber and polyolefin. Preferably, the conductive agent is conductive carbon black, and the binder is polytetrafluoroethylene (dissolved by adding NMP nitrogen-methyl pyrrolidone). The positive current collector comprises one of carbon-coated aluminum foil, copper foil, iron foil, tin foil, zinc foil, nickel foil, titanium foil and manganese foil or an alloy thereof or a compound of any one of the metals or an alloy of any one of the metals. Preferably, the positive electrode current collector is a carbon-coated aluminum foil. The negative current collector comprises one of aluminum, copper, tin, zinc, lead, antimony, cadmium, gold, bismuth, germanium and the like or the alloy or the composite material; preferably, the negative electrode current collector is a copper foil.
In the present invention, the solvent in the electrolytic solution is not particularly limited as long as the solvent can dissociate the electrolyte into cations and anions, and the cations and anions can freely migrate. For example, the solvent in the embodiment of the present invention includes organic solvents such as esters, sulfones, ethers, nitriles, or ionic liquids. Specifically, Propylene Carbonate (PC), Ethylene Carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), Ethyl Methyl Carbonate (EMC), Methyl Formate (MF), Methyl Acetate (MA), N-Dimethylacetamide (DMA), fluoroethylene carbonate (FEC), Methyl Propionate (MP), Ethyl Propionate (EP), Ethyl Acetate (EA), γ -butyrolactone (GBL), Tetrahydrofuran (THF), 2-methyltetrahydrofuran (2MeTHF), 1, 3-Dioxolane (DOL), 4-methyl-1, 3-dioxolane (4MeDOL), Dimethoxymethane (DMM), 1, 2-Dimethoxypropane (DMP), triethylene glycol dimethyl ether (DG), dimethyl sulfone (MSM), dimethyl ether (DME), Ethylene Sulfite (ES), Propylene Sulfite (PS), and propylene carbonate (DMC), Dimethyl sulfite (DMS), diethyl sulfite (DES), crown ether (12-crown-4), 1-ethyl-3-methylimidazole-hexafluorophosphate, 1-ethyl-3-methylimidazole-tetrafluoroborate, 1-ethyl-3-methylimidazole-bistrifluoromethylsulfonyl imide salt, 1-propyl-3-methylimidazole-hexafluorophosphate, 1-propyl-3-methylimidazole-tetrafluoroborate, 1-propyl-3-methylimidazole-bistrifluoromethylsulfonyl imide salt, 1-butyl-1-methylimidazole-hexafluorophosphate, 1-butyl-1-methylimidazole-tetrafluoroborate, 1-butyl-1-methylimidazole-bistrifluoromethylsulfonyl imide salt, di (N-methyl-ethyl-3-methyl-3-imidazole-tetrafluoroborate), di (N-methyl-imidazole-bis (N-fluoro-methyl-sulfonyl) imide salt, di (N-methyl-imidazole-, One or more of N-butyl-N-methylpyrrolidine-bis-trifluoromethylsulfonyl imide salt, 1-butyl-1-methylpyrrolidine-bis-trifluoromethylsulfonyl imide salt, N-methyl-N-propylpyrrolidine-bis-trifluoromethylsulfonyl imide salt, N-methyl, propylpiperidine-bis-trifluoromethylsulfonyl imide salt and N-methyl, butylpiperidine-bis-trifluoromethylsulfonyl imide salt. Preferably, the electrolyte solvent is selected from EC ethylene carbonate, DMC dimethyl carbonate, EMC ethyl methyl carbonate.
In the embodiment of the present invention, the diionic cell is a potassium ion cell, and the potassium salt as the electrolyte is not particularly limited as long as it can be dissociated into cations and anions, and examples thereof include potassium hexafluorophosphate, potassium chloride, potassium fluoride, potassium sulfate, potassium carbonate, potassium phosphate, potassium nitrate, potassium difluoroborate, potassium pyrophosphate, potassium dodecylbenzenesulfonate, potassium dodecylsulfate, tripotassium citrate, potassium metaborate, potassium borate, potassium molybdate, potassium tungstate, potassium bromide, potassium nitrite, potassium iodate, potassium iodide, potassium silicate, potassium lignosulfonate, potassium oxalate, potassium aluminate, potassium methanesulfonate, potassium acetate, potassium dichromate, potassium hexafluoroarsenate, potassium tetrafluoroborate, potassium perchlorate, potassium trifluoromethanesulfonimide (KTFSI), KCF, potassium tetrafluoroborate, potassium trifluoromethanesulfonylimide (KTFSI), and the like3SO3、KN(SO2CF3)2And the concentration ranges from 0.1 mol/L to 10 mol/L. Preference is given toPreferably, the electrolyte potassium salt is potassium hexafluorophosphate.
Furthermore, the components of the separator used in the novel potassium double-ion battery provided by the embodiment of the invention are an insulating porous polymer film or an inorganic porous film, and one or more of a porous polypropylene film, a porous polyethylene film, a porous composite polymer film, glass fiber paper or a porous ceramic separator can be selected. Preferably, the separator is a fiberglass paper.
A schematic structural diagram of a bi-ion battery is shown in fig. 2 (a shell is not shown), and the bi-ion battery comprises a positive electrode current collector 1, a positive electrode active layer 2, an electrolyte 3, a diaphragm 4, a negative electrode active layer 5 and a negative electrode current collector 6. The negative active material in the negative active layer 5 is the high-nitrogen-doped carbon nanosheet prepared by the preparation method. The electrolyte comprises an electrolyte and a solvent, wherein the electrolyte comprises one of potassium salts; the solvent comprises one or more of ester, sulfone, ether organic solvents or ionic liquid. The preferred electrolyte potassium salt is potassium hexafluorophosphate and the electrolyte solvent is selected from EC ethylene carbonate, DMC dimethyl carbonate.
The preparation process comprises the following steps:
the embodiment of the invention also provides a method for preparing a dual-ion battery by using the high-nitrogen-doped carbon nanosheet active material, which comprises the following steps:
step 1: preparing a negative electrode, weighing a negative electrode active material, a conductive agent and a binder according to a certain proportion, adding the negative electrode active material, the conductive agent and the binder into a proper solvent, and fully mixing to obtain uniform slurry to prepare negative electrode active slurry; cleaning a negative current collector, uniformly coating the negative active slurry on the surface of the negative current collector to form a negative active layer, and cutting after the negative active layer is completely dried to obtain the battery negative electrode with the required size;
step 2: preparing an electrolyte: weighing a certain amount of electrolyte (such as potassium salt electrolyte) and adding into corresponding solvent, and stirring thoroughly to dissolve.
And step 3: preparing a diaphragm: cutting the diaphragm into required size, and cleaning.
And 4, step 4: preparing a positive electrode, weighing a positive electrode active material, a conductive agent and a binder according to a certain proportion, adding into a proper solvent, and fully mixing to obtain uniform slurry to prepare positive electrode active slurry; cleaning a positive current collector, uniformly coating the positive active slurry on the surface of the positive current collector to form a positive active layer, and cutting after the positive active layer is completely dried to obtain a battery positive electrode with a required size;
and 5: and assembling the battery cathode, the electrolyte, the diaphragm and the battery anode.
The negative active material prepared by the preparation method of the high-doped nitrogen-carbon nanosheet provided by the embodiment of the invention can overcome the defects of unstable structure, poor cycle stability, more side reactions between the material and electrolyte and low ionic and electronic conductivity of the negative active material of the secondary battery.
The invention is described in further detail with reference to a part of the test results, which are described in detail below with reference to specific examples.
Example 1
The preparation method of the nitrogen-doped carbon nanosheet comprises the following specific steps:
(1) pretreatment (dissolution of sample): taking 200ml of water: pouring the mixed solution of ethanol (the volume ratio is 1:3) into a beaker, uniformly mixing, weighing 1g of citric acid and 10g of urea, adding into the solution, stirring on a magnetic stirring heater until the solution is clear, then heating in a water bath at 75 ℃ for 5h, fully reacting, and drying in an oven at 100 ℃ for 12h to obtain the precursor.
(2) And putting the precursor into a corundum porcelain boat, and covering. Placing the mixture into a tube furnace, sealing the furnace, introducing 30 mm of argon, removing air in the tube, and heating the tube furnace in two steps to obtain a target product: firstly, heating to 350 ℃, and preserving heat for 2 hours, wherein the heating rate is 2 ℃/mim; and then heating to 650 ℃, preserving the heat for 4 hours, wherein the heating rate is 5 ℃/mim, and obtaining the final product of the nitrogen-doped carbon nanosheet with high nitrogen content.
The potassium double-ion battery comprises a negative electrode, electrolyte, a diaphragm and a positive electrode, wherein the positive electrode comprises a positive current collector and a positive active layer, the negative electrode comprises a negative current collector and a negative active layer, and the negative active layer contains the high-nitrogen-doped carbon nanosheet material prepared by the method.
Preparing a negative electrode: adding 0.8g of the prepared nitrogen-doped carbon nanosheet material, 0.1g of acetylene carbon black and 0.1g of polytetrafluoroethylene into 2ml of nitrogen methyl pyrrolidone solution, and fully grinding to obtain uniform slurry; and cleaning the copper foil of the negative current collector, uniformly coating the slurry on the surface of the copper foil (namely the negative current collector) and cleaning the copper foil in vacuum, drying the copper foil to obtain a pole piece, cutting the pole piece into a wafer material layer with the diameter of 12mm, and compacting the wafer material layer to obtain the battery negative electrode for later use.
Preparing an electrolyte: 0.92035g of potassium hexafluorophosphate is weighed and added into a mixed solvent of 5ml of ethylene carbonate (2.3173g) and dimethyl carbonate (1.7317g) methyl ethyl carbonate (1.1564g) (mass ratio, ethylene carbonate: dimethyl carbonate: methyl ethyl carbonate ratio is about: 4:3:2), stirred until the potassium hexafluorophosphate is completely dissolved, added with a potassium salt molecular sieve, and fully and uniformly stirred to be used as electrolyte for standby.
Preparing a diaphragm: the glass fiber film was cut into a circular sheet having a diameter of 16mm and used as a separator.
Preparing a battery positive electrode: adding 0.8g of Expanded Graphite (EG), 0.1g of acetylene black and 0.1g of polytetrafluoroethylene into 2ml of nitrogen methyl pyrrolidone solution, and fully grinding to obtain uniform slurry; and cleaning the positive current collector carbon-coated aluminum foil, uniformly coating the slurry on the surface of the carbon-coated aluminum foil, and drying in vacuum. Cutting the dried electrode slice into a wafer material layer with the diameter of 10 mm; and compacting to obtain the positive electrode of the battery for later use.
Assembling the battery: and (3) setting the box body pressure to be between-1 and 5Pa in a glove box protected by inert gas, tightly stacking the prepared cathode, the diaphragm and the anode in sequence, dripping electrolyte to completely soak the diaphragm, and packaging the stacked part into a button cell shell to finish cell assembly.
Examples 2 to 14
Examples 2 to 14 were the same as example 1, except that the organic acid, the organic primary amine, and the mixed solvent in the preparation of the nitrogen-doped carbon nanosheet material were different from those in comparative example 1 (see table 1).
TABLE 1
Examples 15 to 22
Examples 15 to 22 were the same as example 1, except that the precursor formation temperature parameters in the preparation of the nitrogen-doped carbon nanosheet material were different from those in comparative example 1 (see table 2).
TABLE 2
Examples 23 to 29
In examples 22 to 29, the same procedure as in example 1 was repeated, except that the calcination carbonization temperature parameters of the nitrogen-doped carbon nanosheet material were different from those of comparative example 1 (see table 3).
TABLE 3
Examples 31 to 54
In examples 31 to 54, the same as example 1 was conducted except that the positive electrode active material, separator or electrolyte solvent of the bipolar battery was different from that of comparative example 1 (see table 4).
TABLE 4
Performance testing
The electrochemical performance test of the double-ion battery provided by the embodiment comprises the following steps of cycle number, capacity retention rate and coulombic efficiency:
and (3) cyclic charge and discharge: the method is characterized in that cyclic charging and discharging are carried out on a CT2001C-001 blue battery cyclic testing system, the standard capacity of an electrode is tested by charging and discharging at a rate of 100mA/g, the specific capacity of a material is current time/sample mass, the energy density of the material is the specific capacity of the material and the platform voltage of the battery, the charging and discharging conditions are determined according to the needs of experiments, and the cyclic step comprises the following steps: standing for 60 s-constant current discharging-standing for 60 s-constant current charging.
Multiplying power charge and discharge: the method is also carried out on a blue-ray battery cycle test system, the rate performance of the material is tested by charging and discharging at different rates (current density), the charging and discharging conditions depend on the needs of experiments, and the cycle steps are the same as the cycle charging and discharging.
The results are shown in Table 5.
TABLE 5
From the data in table 5, it can be seen that: example 1 is the best case explored in the experimental process of the invention.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A preparation method of nitrogen-doped carbon nanosheets is characterized by comprising the following steps:
providing an organic acid and an organic primary amine, wherein the organic acid contains a carboxyl group;
dissolving the organic acid and the organic primary amine in a solvent for heating treatment, and then drying to obtain a precursor;
and calcining and carbonizing the precursor to obtain the nitrogen-doped carbon nanosheet.
2. A method of making nitrogen doped carbon nanoplatelets as in claim 1 wherein the calcining carbonization process comprises: the temperature is raised to 400 ℃ for the first heat preservation, and then raised to 750 ℃ for the second heat preservation.
3. A method of making nitrogen doped carbon nanoplatelets as in claim 2 wherein the first incubation time is between 2 and 5 hours; and/or the presence of a gas in the gas,
the second heat preservation time is 3-6 h; and/or the presence of a gas in the gas,
the heating rate is 2-5 ℃/555 during the calcining carbonization process; and/or the presence of a gas in the gas,
the calcination carbonization is carried out in an inert atmosphere.
4. A method of making nitrogen-doped carbon nanoplatelets as in claim 1 wherein the heating treatment is water bath heating; and/or the presence of a gas in the gas,
the temperature of the heating treatment is 40-85 ℃; and/or
The time of the heating treatment is 3-7 h; and/or the presence of a gas in the gas,
the drying temperature is 70-120 ℃, and/or;
the drying time is 6-13 h; and/or the presence of a gas in the gas,
the mass ratio of the organic acid to the organic primary amine is 1 (5-15).
5. A method of making nitrogen doped carbon nanoplatelets according to any of claims 1-4 wherein the organic acid comprises a hydroxy acid; and/or the presence of a gas in the gas,
the organic primary amine comprises at least one of acetamide, propionamide and urea; and/or the presence of a gas in the gas,
the solvent is a mixed solvent of alcohol and water.
6. A method of making nitrogen doped carbon nanoplatelets according to claim 5 wherein the hydroxy acid comprises at least one of citric acid, glycolic acid, tartaric acid, malic acid and lactic acid; and/or the presence of a gas in the gas,
the alcohol in the solvent comprises at least one of methanol, ethanol, ethylene glycol and propanol; and/or the presence of a gas in the gas,
the volume ratio of alcohol to water in the solvent is (1-10): 1.
7. An anode active material, wherein the anode active material is a nitrogen-doped carbon nanosheet obtained by the preparation method according to any one of claims 1 to 6.
8. A negative electrode includes a negative electrode current collector and a negative electrode active layer bonded to a surface of the negative electrode current collector, the negative electrode active layer containing a negative electrode active material, a conductive agent, and a binder; characterized in that the negative electrode active material comprises nitrogen-doped carbon nanosheets obtained by the preparation method of any one of claims 1 to 6.
9. A bi-ion battery comprising a positive electrode, a negative electrode, and a separator and an electrolyte between the positive electrode and the negative electrode, wherein the negative electrode is the negative electrode of claim 8.
10. The bi-ion battery of claim 9, wherein the bi-ion battery comprises any one of a lithium ion battery, a sodium ion battery, a potassium ion battery, a calcium ion battery, a magnesium ion battery, and a zinc ion battery.
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