CN114094061A - Rice-grain-shaped manganese carbonate composite graphene high-performance lithium storage material and lithium battery - Google Patents
Rice-grain-shaped manganese carbonate composite graphene high-performance lithium storage material and lithium battery Download PDFInfo
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- CN114094061A CN114094061A CN202111177995.5A CN202111177995A CN114094061A CN 114094061 A CN114094061 A CN 114094061A CN 202111177995 A CN202111177995 A CN 202111177995A CN 114094061 A CN114094061 A CN 114094061A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 74
- 239000011656 manganese carbonate Substances 0.000 title claims abstract description 68
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 title claims abstract description 68
- 235000006748 manganese carbonate Nutrition 0.000 title claims abstract description 66
- 229940093474 manganese carbonate Drugs 0.000 title claims abstract description 66
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 title claims abstract description 66
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 48
- 239000011232 storage material Substances 0.000 title claims abstract description 41
- 239000002245 particle Substances 0.000 claims abstract description 34
- 239000002243 precursor Substances 0.000 claims abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000002696 manganese Chemical class 0.000 claims abstract description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 7
- 150000007524 organic acids Chemical class 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 62
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 12
- 239000001099 ammonium carbonate Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 10
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- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
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- 238000005303 weighing Methods 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000011889 copper foil Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 235000003704 aspartic acid Nutrition 0.000 claims description 5
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 5
- 229960004889 salicylic acid Drugs 0.000 claims description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
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- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical group [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 229960005261 aspartic acid Drugs 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
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- 235000015165 citric acid Nutrition 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
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- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 6
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- 231100000252 nontoxic Toxicity 0.000 abstract description 2
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- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
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- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
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- 238000003917 TEM image Methods 0.000 description 2
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- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000005323 carbonate salts Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- -1 small molecule organic acid Chemical class 0.000 description 1
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- 229910000299 transition metal carbonate Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
The invention belongs to the technical field of lithium battery electrode materials, and particularly relates to a rice-grain manganese carbonate composite graphene high-performance lithium storage material and a lithium battery. According to the invention, a simple step-by-step hydrothermal reaction method is adopted, water is used as a solvent, a certain amount of soluble manganese salt is used as a raw material to synthesize a precursor at room temperature, then carbonate is added to be used as a precipitating agent, graphene and small molecular organic acid, and the nano-scale rice-shaped manganese carbonate composite graphene high-performance lithium storage material is synthesized through a hydrothermal one-step reaction. The product prepared by the method has regular shape, uniform size and uniform particle size distribution, compared with the existing report, the method is simple and easy to control, is non-toxic and harmless, and is easier for large-scale production and popularization, and the size of the rice-shaped manganese carbonate nanoparticles is smaller than that of the conventional one-step hydrothermal synthesis, so that the structure of the rice-shaped manganese carbonate nanoparticles has high structural stability, large specific surface area, high surface activity and short ion transmission distance, and higher capacity and better circulation stability can be provided for the lithium ion battery.
Description
Technical Field
The invention belongs to the technical field of lithium battery electrode materials, and particularly relates to a rice-grain manganese carbonate composite graphene high-performance lithium storage material and a lithium battery.
Background
Nowadays, the environmental pollution problem caused by the gradual exhaustion and excessive consumption of fossil fuel is a difficult problem to be solved urgently. Under such a background, rechargeable Lithium Ion Batteries (LIBs) have been widely studied for their high energy density, long cycle life, and good environmental friendliness, and have been commercially used in portable electronic products. However, commercial graphite negative electrodes are due to their low theoretical capacity (372 mAhg only)-1) And the growing demand cannot be met, and the development of the LIB in high-energy equipment such as an electric vehicle and a smart grid is greatly limited. Therefore, the search for a novel anode material with high specific capacity is of great significance at present.
Transition metal carbonates (TMC for short) are a new class of conversion-type LIB anode materials, and are widely concerned by people due to their advantages of low cost, easy preparation, high theoretical capacity, etc. Among them, manganese (mainly in the form of pyrolusite) is one of the most popular candidate elements because of its abundant natural reserves. Due to its eco-friendliness, low production cost (manganese is about 20 times lower than cobalt), lower operating voltage, and higher output voltage and energy density, it is considered to be a novel high-capacity anode material with promising application prospect. However, during lithiation and delithiation, MnCO3Poor conductivity, slow ion transport kinetics and large volume changes leading to unsatisfactory rate capability and poor cycling performance, which becomes MnCO3Major obstacles to the use in practical LIBs. Currently, three typical strategies have proven to be effective approaches to the problem of negative electrode materials. The first is to synthesize nano-scale negative electrode materials such as nano-sheets, nano-rods and nano-spheres, which can effectively reduce particlesThe volume of the particles expands, preventing pulverization of the particles, and also enlarging the contact area of the active material with the electrolyte and shortening the ion diffusion path. The second is heteroatom doping including metal element doping such as Ni, Co, Fe and Zn, or nonmetal element doping such as N and B, so that intrinsic electron conductivity of the anode material can be improved; the last one is that a negative electrode material and a conductive additive (such as graphene and carbon nano tubes) are combined to form a composite material, and a carbon material with good electronic conductivity can be used as a bridge for electron transfer, so that the electrochemical performance is remarkably improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a rice-shaped manganese carbonate composite graphene high-performance lithium storage material and a lithium battery.
The technical scheme adopted by the invention is as follows: the preparation method of the rice-grain-shaped manganese carbonate composite graphene high-performance lithium storage material comprises the following steps:
s1, dissolving manganese salt and alkali in water, stirring for reaction, washing and centrifuging reaction liquid after the reaction is finished to obtain precursor particles;
s2, stirring the precursor particles obtained in the step S1 with graphene, carbonate and small molecular organic acid for 10-30 min to react, sealing the mixture in a reaction kettle, placing the reaction kettle in an oven to react, and cooling the reaction kettle to room temperature after the reaction is finished; and (3) discarding the supernatant in the reaction kettle, washing the product with ethanol and water, and freeze-drying to obtain the rice-shaped manganese carbonate composite graphene high-performance lithium storage material.
As a further technical scheme, the soluble manganese salt is manganese sulfate, manganese nitrate, manganese chloride or manganese acetate.
As a further technical scheme, the alkali is sodium hydroxide or potassium hydroxide.
As a further technical scheme, the carbonate is sodium carbonate, sodium bicarbonate, ammonium carbonate or ammonium bicarbonate.
As a further technical scheme, the small molecular organic acid is citric acid, ascorbic acid, aspartic acid or salicylic acid.
As a further technical scheme, in the step S2, the reaction in the oven is 110-180 ℃.
As a further technical scheme, in the step S2, the reaction time in the oven is 0.5-18 h.
As a further technical scheme, the particle size of the rice-shaped manganese carbonate composite graphene high-performance lithium storage material is 500 +/-200 nanometers.
The invention further provides a lithium ion battery containing the rice-shaped manganese carbonate composite graphene high-performance lithium storage material.
As a further technical scheme, the preparation method comprises the following steps:
(A) weighing a rice-grain-shaped manganese carbonate composite graphene material, acetylene black and sodium alginate, adding a certain amount of distilled water, uniformly mixing, grinding and stirring into paste, and coating the paste on a copper foil;
(B) and drying, slicing and assembling the coated copper foil of the rice-grain-shaped manganese carbonate composite graphene lithium storage material to obtain the lithium ion battery.
The invention has the following beneficial effects: according to the invention, a simple step-by-step hydrothermal reaction method is adopted, water is used as a solvent, a certain amount of soluble manganese salt is used as a raw material to synthesize a precursor at room temperature, then a certain amount of carbonate is added to be used as a precipitator, a certain amount of graphene and small molecular organic acid are added, and after sealing, the rice-shaped manganese carbonate composite graphene high-performance lithium storage material with nano scale is synthesized through hydrothermal one-step reaction at a certain temperature for a certain time.
The high-performance lithium storage material of the rice-grain manganese carbonate composite graphene prepared by the invention has the advantages of regular shape, uniform size and uniform particle size distribution, compared with the existing reports, the method disclosed by the invention is simple and easy to control, is non-toxic and harmless, and is easier to produce and popularize on a large scale, and the size of the rice-grain manganese carbonate nanoparticles is smaller than that of the conventional one-step hydrothermal synthesis, so that the structure of the rice-grain manganese carbonate composite graphene has high structural stability, large specific surface area, high surface activity and short ion transmission distance, and thus higher capacity and better cycling stability can be provided for a lithium ion battery.
In some embodiments of the invention, at 100mA g-1At a current density of (2), charging and dischargingThe battery capacity after 50 circles is stabilized at 1269 mAh g-1And the conventionally synthesized manganese carbonate particle composite graphene is at 100mA g-1The battery capacity after charging and discharging for 50 circles is stabilized at 292 mAh g under the current density of (1)-1(ii) a Even at 1A g-1The capacity after charging and discharging for 500 circles is still stabilized at 1040 mAh g under the high current density of (1)-1(ii) a While the conventionally synthesized manganese carbonate particle composite graphene is 1A g-1The battery capacity after charging and discharging for 500 circles is stabilized at 80 mAh g under the current density of (1)-1. It can be seen that the rice-shaped manganese carbonate composite graphene high-performance lithium storage material has higher capacity and better cycle stability.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is within the scope of the present invention for those skilled in the art to obtain other drawings based on the drawings without inventive exercise.
Fig. 1 (a) TEM images of conventional synthesis of spherical manganese carbonate particle composite graphene (b) TEM images of stepwise synthesis of rice-grain manganese carbonate composite graphene;
FIG. 2 is a graph showing XRD diffraction results of conventional synthesized spherical manganese carbonate particle composite graphene and stepwise synthesized rice-shaped manganese carbonate composite graphene high-performance lithium storage materials and comparison thereof with standard data (PDF #44-1472) of manganese carbonate crystals;
FIG. 3 is SEM pictures (a, c low-power pictures; b, d high-power pictures) of conventionally synthesized spherical manganese carbonate particle composite graphene (a, b) and synthesized rice-shaped manganese carbonate composite graphene high-performance lithium storage materials (c, d) step by step;
FIG. 4 shows that the conventional synthesis of spherical manganese carbonate particle composite graphene (black square) and the stepwise synthesis of rice-shaped manganese carbonate composite graphene high-performance lithium storage material (green sphere) are carried out at 100mA g-1A cycle stability test plot at current density;
FIG. 5 conventional synthetic spherical carbonThe manganese acid particle composite graphene (black square) and the step-by-step synthesis of the rice-shaped manganese carbonate composite graphene high-performance lithium storage material (green spherical) are 1A g-1Graph of cycling stability at current density.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
A rice-grain manganese carbonate composite graphene high-performance lithium storage material is prepared by the following steps:
s1, dissolving manganese salt and alkali in water according to a certain proportion, stirring and reacting at room temperature, washing and centrifuging reaction liquid after the reaction is finished to obtain precursor particles;
s2, stirring the precursor particles obtained in the step S1 with graphene, carbonate and small molecular organic acid at room temperature for 10-30 min to react, sealing the mixture in a reaction kettle, placing the reaction kettle in an oven to react for a certain time, and cooling the reaction kettle to room temperature after the reaction is finished; and (3) discarding the supernatant in the reaction kettle, washing the product with ethanol and water, freezing and drying to obtain a final product, namely the rice-shaped manganese carbonate composite graphene high-performance lithium storage material, and finally assembling the lithium ion battery.
In some embodiments of the invention, the soluble manganese salt of step S1 is manganese sulfate, manganese nitrate, manganese chloride, or manganese acetate.
In some embodiments of the invention, the base of step S1 is sodium hydroxide or potassium hydroxide.
In some embodiments of the present invention, the reaction time of step S1 is 1-12 h.
In some embodiments of the invention, the carbonate salt in step S2 is sodium carbonate, sodium bicarbonate, ammonium carbonate, or ammonium bicarbonate.
In some embodiments of the invention, the small molecule organic acid of step S2 is citric acid, ascorbic acid, aspartic acid, or salicylic acid.
In some embodiments of the present invention, the oven temperature of step S2 is 110-180 ℃.
In some embodiments of the present invention, the reaction time of step S2 is 0.5-18 h.
In some embodiments of the invention, the rice-shaped manganese carbonate nanoparticles have a particle size of 500 ± 200 nanometers.
The invention also provides a lithium ion battery assembled by the rice-grain manganese carbonate composite graphene high-performance lithium storage material, and the preparation method comprises the following steps:
(A) weighing a rice-shaped manganese carbonate composite graphene material, acetylene black and sodium alginate, adding a proper amount of distilled water, uniformly mixing, grinding and stirring into paste, and coating the paste on a copper foil;
(B) and drying, slicing and assembling the coated copper foil of the rice-grain-shaped manganese carbonate composite graphene lithium storage material to obtain the lithium ion battery.
The following are some examples of the invention.
Example 1
S1, adding 0.245g of manganese acetate and 0.6g of sodium hydroxide into 300mL and 10mL of ultrapure water respectively, stirring until the solution is clear, dropwise adding the sodium hydroxide solution into the manganese acetate solution, stirring and reacting at room temperature for 12 hours, washing the reaction solution after the reaction is finished, and centrifuging to obtain precursor particles;
s2, placing the precursor particles obtained in the step S1 and 10mL of graphene (2.6 g/L) in a reaction kettle, ultrasonically mixing for 10min, respectively weighing 0.4g of ammonium bicarbonate and 0.2g of ascorbic acid, adding the mixture into the graphene mixed solution, stirring at room temperature for 20min for reaction, sealing the reaction kettle, placing the reaction kettle in a 180 ℃ drying oven for reaction for 15h, and cooling the reaction kettle to room temperature after the reaction is finished; and (3) discarding the supernatant in the reaction kettle, washing the product with ethanol and water, freezing and drying to obtain a final product, namely the rice-shaped manganese carbonate composite graphene high-performance lithium storage material, and finally assembling the lithium ion battery.
Example 2
S1, adding 0.245g of manganese sulfate and 0.6g of potassium hydroxide into 300mL and 10mL of ultrapure water respectively, stirring until the solution is clear, dropwise adding a sodium hydroxide solution into a manganese acetate solution, stirring and reacting at room temperature for 12 hours, washing a reaction solution after the reaction is finished, and centrifuging to obtain precursor particles;
s2, placing the precursor particles obtained in the step S1 and 10mL of graphene (2.6 g/L) in a reaction kettle, ultrasonically mixing for 10min, respectively weighing 0.4g of ammonium bicarbonate and 0.2g of aspartic acid, adding the ammonium bicarbonate and the aspartic acid into the graphene mixed solution, stirring at room temperature for 20min for reaction, sealing the reaction kettle, placing the reaction kettle in a 190 ℃ drying oven for reaction for 15h, and cooling the reaction kettle to room temperature after the reaction is finished; and (3) discarding the supernatant in the reaction kettle, washing the product with ethanol and water, freezing and drying to obtain a final product, namely the rice-shaped manganese carbonate composite graphene high-performance lithium storage material, and finally assembling the lithium ion battery.
Example 3
S1, adding 0.245g of manganese nitrate and 0.6g of sodium hydroxide into 300mL and 10mL of ultrapure water respectively, stirring until the solution is clear, dropwise adding the sodium hydroxide solution into the manganese acetate solution, stirring and reacting at room temperature for 12 hours, washing the reaction solution after the reaction is finished, and centrifuging to obtain precursor particles;
s2, placing the precursor particles obtained in the step S1 and 10mL of graphene (2.6 g/L) in a reaction kettle, ultrasonically mixing for 10min, respectively weighing 0.4g of sodium bicarbonate and 0.2g of citric acid, adding the sodium bicarbonate and the citric acid into the graphene mixed solution, stirring at room temperature for 20min for reaction, sealing the reaction kettle, placing the reaction kettle in a 170 ℃ drying oven for reaction for 15h, and cooling the reaction kettle to room temperature after the reaction is finished; and (3) discarding the supernatant in the reaction kettle, washing the product with ethanol and water, freezing and drying to obtain a final product, namely the rice-shaped manganese carbonate composite graphene high-performance lithium storage material, and finally assembling the lithium ion battery.
Example 4
S1, adding 0.2g of manganese chloride and 0.6g of potassium hydroxide into 300mL and 10mL of ultrapure water respectively, stirring until the solution is clear, dropwise adding a sodium hydroxide solution into a manganese acetate solution, stirring and reacting at room temperature for 12 hours, washing and centrifuging a reaction solution after the reaction is finished to obtain precursor particles;
s2, placing the precursor particles obtained in the step S1 and 10mL of graphene (2.6 g/L) in a reaction kettle, ultrasonically mixing for 10min, respectively weighing 0.4g of ammonium bicarbonate and 0.2g of salicylic acid, adding the ammonium bicarbonate and the salicylic acid into the graphene mixed solution, stirring at room temperature for 20min for reaction, sealing the reaction kettle, placing the reaction kettle in a 160 ℃ drying oven for reaction for 15h, and cooling the reaction kettle to room temperature after the reaction is finished; and (3) discarding the supernatant in the reaction kettle, washing the product with ethanol and water, freezing and drying to obtain a final product, namely the rice-shaped manganese carbonate composite graphene high-performance lithium storage material, and finally assembling the lithium ion battery.
Comparative example 1:
the lithium storage material of manganese carbonate composite graphene is synthesized by a conventional one-step hydrothermal method by taking 0.245g of manganese acetate, 0.4g of ammonium carbonate and 10mL of graphene (2.6 g/L) as raw materials.
In comparative example 1, the spherical manganese carbonate particle composite graphene synthesized by the conventional method is compared with the rice-grain manganese carbonate particle composite graphene synthesized by the example 1 step by step, and fig. 1-3 are comparison of appearance characterization results of the spherical manganese carbonate particle composite graphene and the rice-grain manganese carbonate particle composite graphene, so that the manganese carbonate particle materials synthesized by the two methods are pure in phase and good in crystallinity, but the size of the rice-grain manganese carbonate nanoparticles is smaller than that of the conventional one-step hydrothermal synthesis. Fig. 4-5 are comparison of electrochemical performances of the two materials, and it can be seen that the rice-shaped manganese carbonate composite graphene high-performance lithium storage material has higher capacity and better cycle stability. Example 1 the prepared rice-shaped manganese carbonate nanoparticles were at 100mA g-1The battery capacity after 50 cycles of charging and discharging is stabilized at 1269 mAh g under the current density of (A)-1And the conventionally synthesized manganese carbonate particle composite graphene is at 100mA g-1The battery capacity after charging and discharging for 50 circles is stabilized at 292 mAh g under the current density of (1)-1(ii) a Even at 1A g-1The capacity after charging and discharging for 500 circles is still stabilized at 1040 mAh g under the high current density of (1)-1(ii) a While the conventionally synthesized manganese carbonate particle composite graphene is 1A g-1The battery capacity after charging and discharging for 500 circles is stabilized at 80 mAh g under the current density of (1)-1。
The morphology characterization and the electrochemical performance of the rice-shaped manganese carbonate composite graphene high-performance lithium storage material prepared in the embodiments 2 to 4 are similar to those of the product prepared in the embodiment 1.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.
Claims (10)
1. The rice-grain-shaped manganese carbonate composite graphene high-performance lithium storage material is characterized in that the preparation method comprises the following steps:
s1, dissolving manganese salt and alkali in water, stirring for reaction, washing and centrifuging reaction liquid after the reaction is finished to obtain precursor particles;
s2, stirring the precursor particles obtained in the step S1 with graphene, carbonate and small molecular organic acid for 10-30 min to react, sealing the mixture in a reaction kettle, placing the reaction kettle in an oven to react, and cooling the reaction kettle to room temperature after the reaction is finished; and (3) discarding the supernatant in the reaction kettle, washing the product with ethanol and water, and freeze-drying to obtain the rice-shaped manganese carbonate composite graphene high-performance lithium storage material.
2. The rice-shaped manganese carbonate composite graphene high-performance lithium storage material according to claim 1, wherein: the soluble manganese salt is manganese sulfate, manganese nitrate, manganese chloride or manganese acetate.
3. The rice-shaped manganese carbonate composite graphene high-performance lithium storage material according to claim 1, wherein: the alkali is sodium hydroxide or potassium hydroxide.
4. The rice-shaped manganese carbonate composite graphene high-performance lithium storage material according to claim 1, wherein: the carbonate is sodium carbonate, sodium bicarbonate, ammonium carbonate or ammonium bicarbonate.
5. The rice-shaped manganese carbonate composite graphene high-performance lithium storage material according to claim 1, wherein: the small molecular organic acid is citric acid, ascorbic acid, aspartic acid or salicylic acid.
6. The rice-shaped manganese carbonate composite graphene high-performance lithium storage material according to claim 1, wherein: in step S2, the reaction in the oven is 110-180 ℃.
7. The rice-shaped manganese carbonate composite graphene high-performance lithium storage material according to claim 1, wherein: in step S2, the reaction time in the oven is 0.5-18 h.
8. The rice-shaped manganese carbonate composite graphene high-performance lithium storage material according to claim 1, wherein: the grain size of the rice-shaped manganese carbonate composite graphene high-performance lithium storage material is 500 +/-200 nanometers.
9. A lithium ion battery containing the rice-shaped manganese carbonate composite graphene high-performance lithium storage material as defined in any one of claims 1 to 8.
10. The lithium ion battery according to claim 9, characterized in that its preparation method comprises the following steps:
(A) weighing a rice-grain-shaped manganese carbonate composite graphene material, acetylene black and sodium alginate, adding a certain amount of distilled water, uniformly mixing, grinding and stirring into paste, and coating the paste on a copper foil;
(B) and drying, slicing and assembling the coated copper foil of the rice-grain-shaped manganese carbonate composite graphene lithium storage material to obtain the lithium ion battery.
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