CN111063874B - Preparation method and application of hard carbon nano material for ion battery - Google Patents
Preparation method and application of hard carbon nano material for ion battery Download PDFInfo
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Abstract
The invention relates to the field of carbon nano materials, in particular to a preparation method and application of a hard carbon nano material for an ion battery. The invention discloses a preparation method of a hard carbon nano material for an ion battery, which is characterized by comprising the following steps of: step 1, preparing hard carbon pretreatment liquid; step 2, preparing nano zirconium silicide; step 3, preparing modified nano zirconium silicide; and 4, preparing the hard carbon nano material. The invention solves the defects of low capacity, low first efficiency, low capability of rapidly inserting/extracting lithium/sodium and the like of the hard carbon cathode material in the prior art. The prepared modified nano zirconium silicide is combined with the treated waste fruit core, and the obtained hard carbon nano material not only has the advantage of higher capacity than common hard carbon, but also overcomes the defects of low primary efficiency and low rapid ion intercalation/deintercalation capability of common hard carbon.
Description
Technical Field
The invention relates to the field of carbon nano materials, in particular to a preparation method and application of a hard carbon nano material for an ion battery.
Background
With the great progress and rapid development of the information age, multifunctional portable electronic equipment, electric automobiles, aircrafts, artificial power assistance and other equipment put higher requirements on energy storage materials. Therefore, the research and development of novel lithium battery electrode materials with high specific capacity, high rate, high safety and the like are urgent.
At present, the traditional carbon negative electrode material mainly comprises artificial graphite, natural graphite, mesocarbon microbeads, soft carbon, hard carbon and the like, wherein the hard carbon is non-graphitizable carbon, and has the advantages of random sequencing, stable structure, long charge-discharge cycle life, better safety performance and the like, and the problems that the reactivity of the graphitized carbon charged into lithiated graphite is high, and once internal short circuit occurs, serious exothermic reaction is caused, and even explosion is caused can be solved. However, the hard carbon negative electrode material in the prior art has the defects of low capacity, low first-time efficiency, low rapid ion intercalation/deintercalation capability and the like.
Disclosure of Invention
In view of the above problems, it is an object of the present invention to provide a method for preparing a hard carbon nanomaterial for an ion battery, comprising the steps of:
step 1, preparing a hard carbon pretreatment solution:
crushing fruit kernels, mixing the crushed fruit kernels with deionized water, and adding concentrated sulfuric acid for carbonization treatment to obtain hard carbon pretreatment liquid;
step 2, preparing nano zirconium silicide:
preparing nano zirconium silicide by using superfine zirconium powder and micro silicon powder;
step 3, preparing modified nano zirconium silicide:
scandium chloride is used for modifying the nano zirconium silicide to obtain modified nano zirconium silicide;
step 4, preparing the hard carbon nano material:
and reacting the modified nano zirconium silicide with the hard carbon pretreatment solution, and pyrolyzing to obtain the hard carbon nano material.
Preferably, the step 1 specifically comprises:
step 1, preparing a hard carbon pretreatment solution:
(1) cleaning fruit kernels, and grinding the fruit kernels into powder to obtain fruit kernel powder;
(2) adding the fruit kernel powder into deionized water, uniformly dispersing, adding concentrated sulfuric acid with the mass concentration of 98%, and uniformly stirring to obtain a hard carbon pretreatment substance;
wherein the solid-to-liquid ratio of the fruit stone powder to the deionized water is 1: 20-30; the mass ratio of concentrated sulfuric acid to fruit kernel powder is 1-2: 10;
(3) and (3) transferring the hard carbon pretreatment substance into a reaction kettle with a polytetrafluoroethylene lining, setting the temperature to be 200-300 ℃, reacting for 24-48 h, and cooling to room temperature to obtain a hard carbon pretreatment liquid.
Preferably, the step 2 specifically comprises:
step 2, preparing nano zirconium silicide:
(1) respectively placing superfine zirconium powder and micro silicon powder in a vacuum drying oven for drying treatment, then uniformly mixing, placing in a graphite furnace, heating to 900-1000 ℃ under the protection of inert gas atmosphere for preheating for 0.5-1 h, introducing hydrogen, gradually heating to 1200-1300 ℃ at the speed of 10 ℃/min, reacting for 5-10 h, and cooling to room temperature to obtain a zirconium silicide crude product;
wherein the mol ratio of the superfine zirconium powder to the micro silicon powder is 1: 2-3;
(2) and adding the zirconium silicide crude product into ethanol, uniformly dispersing, performing ultrasonic treatment for 0.5-1 h, drying, grinding, and crushing in a nano-scale superfine crusher to obtain the nano-zirconium silicide.
Preferably, the step (3) is specifically:
step 3, preparing modified nano zirconium silicide:
(1) weighing scandium chloride, mixing and dissolving with deionized water, adding nano zirconium silicide and a dispersing agent, dispersing uniformly, then dropwise adding a sodium hydroxide solution with the concentration of 0.1mol/L until the pH value of the liquid is 9-10, transferring the liquid to a reaction kettle with a polytetrafluoroethylene lining after dispersing uniformly, setting the temperature to be 150-220 ℃, reacting for 12-18 h, cooling to room temperature, washing for 3 times with acetone, then washing with deionized water to be neutral, and drying at 80-100 ℃ to obtain a modified zirconium silicide precursor;
wherein the solid-to-liquid ratio of scandium chloride to deionized water is 1: 20-30; the mass ratio of the polyethylene glycol to the deionized water is 1-5: 100; the mass ratio of the nano zirconium silicide to the scandium chloride is 8-10: 1;
(2) grinding the modified zirconium silicide precursor into powder, placing the powder in a graphite furnace, heating to 1000-1200 ℃, calcining for 10-12 h, cooling to room temperature, grinding, and placing the powder in a nano-scale superfine crusher for crushing to obtain the modified nano-zirconium silicide.
Preferably, the step (4) is specifically:
step 4, preparing the hard carbon nano material:
(1) adding modified nano zirconium silicide into the hard carbon pretreatment liquid, uniformly dispersing, transferring into a reaction kettle with a polytetrafluoroethylene lining, heating to 200-250 ℃, reacting for 18-24 h, cooling to room temperature, filtering to obtain a solid, washing with acetone for 3 times, then washing with deionized water to be neutral, placing in an oven at 80-100 ℃, and drying for 12-20 h to obtain a hard carbon nano material precursor;
wherein the solid-to-liquid ratio of the modified nano zirconium silicide to the hard carbon pretreatment liquid is 1: 10-20;
(2) and (3) placing the precursor of the hard carbon nano material in a corundum crucible, placing the crucible in a tubular resistance furnace, heating to 500-1000 ℃ at the speed of 5-10 ℃/min under the protection of nitrogen atmosphere, and pyrolyzing for 6-8 hours to obtain the hard carbon nano material.
Preferably, the fruit kernel is one or more of mango kernel, loquat kernel and shea nut kernel.
Preferably, the particle size of the fruit kernel powder is 150-300 μm.
Preferably, the particle size of the nano zirconium silicide is 50-100 nm.
Preferably, in the step (2), the solid-to-liquid ratio of the zirconium silicide crude product to the ethanol is 1: 20-50.
Preferably, the particle size of the modified nano zirconium silicide is 50-100 nm.
The second purpose of the invention is to provide an application of the hard carbon nano material prepared by the method in a sodium ion battery, wherein the specific application is as follows:
the cathode of the sodium ion battery is prepared from the hard carbon nano material.
The process for preparing the cathode of the sodium ion battery by using the hard carbon nano material comprises the following steps: and mixing the hard carbon nano material with a binder according to a mass ratio of 10:1, adding NMP to prepare slurry, coating the slurry on an aluminum foil, and drying to obtain the sodium-ion battery cathode.
Preferably, the adhesive is polyvinylidene fluoride or polytetrafluoroethylene.
The third purpose of the invention is to provide the application of the hard carbon nano material prepared by the method in the lithium ion battery.
The negative electrode of the lithium ion battery is prepared from the hard carbon nano material.
The process for preparing the lithium ion battery cathode by using the hard carbon nano material comprises the following steps: and mixing the hard carbon nano material with a binder according to a mass ratio of 10:1, adding NMP to prepare slurry, coating the slurry on a copper foil, and drying to obtain the lithium ion battery cathode.
Preferably, the adhesive is polyvinylidene fluoride or polytetrafluoroethylene.
The invention has the beneficial effects that:
1. the raw materials used for preparing the hard carbon nano material are derived from waste fruit kernels, mainly comprise mango kernels, shea kernels and loquat kernels, the three fruit kernels contain abundant cellulose and lignin, but the three fruit kernels are not used as a carbon source of a battery material in the prior art.
2. According to the invention, the nano zirconium silicide is prepared firstly, scandium chloride is used for modifying the nano zirconium silicide, and the obtained modified nano zirconium silicide has anisotropy similar to that of a hard carbon material and can perfectly fit with the hard carbon material to play a role. The invention selects zirconium silicide with excellent hardness, high temperature resistance and conductivity to prepare a new hard carbon material, improves the conductivity, hardness and high temperature resistance of the hard carbon material, but the zirconium silicide has low de/intercalation capability for alkali metal ions (mainly lithium ions and sodium ions) due to the structure of the zirconium silicide, but does not achieve the expected effect. Therefore, the invention firstly carries out nanocrystallization on zirconium silicide to improve the specific surface area of the zirconium silicide, and then uses rare earth scandium ions to modify the structure of the zirconium silicide, thereby improving the sodium/lithium storage capacity of the zirconium silicide, reducing the sodium/lithium storage potential of the zirconium silicide and enabling the zirconium silicide to be more easily subjected to deintercalation on alkali metal ions.
3. According to the invention, the prepared modified nano zirconium silicide is combined with the treated waste fruit core, and the obtained hard carbon nano material not only has the advantage of higher capacity than common hard carbon, but also overcomes the defects of low primary efficiency and low rapid ion intercalation/deion capability of common hard carbon. The hard carbon nano material prepared by the invention has the first charge-discharge efficiency of more than 90 percent when being used as a lithium ion battery cathode, has the reversible specific capacity of 387mAh/g, can also reach more than 86 percent when being used as a sodium ion battery cathode, has the reversible specific capacity of 311mAh/g, and has good electrochemical performance; the lithium ion battery or the sodium ion battery has good cycle stability, and the capacity retention rate is over 84% after 500 cycles.
Detailed Description
The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present invention. Rather, they are merely examples of apparatus and methods consistent with certain aspects of the invention, as detailed in the appended claims.
Example 1
A preparation method of a hard carbon nano material for an ion battery comprises the following steps:
step 1, preparing a hard carbon pretreatment solution:
(1) cleaning mango seeds, grinding the mango seeds into powder, and sieving the powder to obtain mango seed powder with the particle size of 150-300 mu m;
(2) adding mango seed powder into deionized water, uniformly dispersing, adding concentrated sulfuric acid with the mass concentration of 98%, and uniformly stirring to obtain a hard carbon pretreatment substance;
wherein the solid-to-liquid ratio of the mango seed powder to the deionized water is 1: 20-30; the mass ratio of concentrated sulfuric acid to mango seed powder is 1-2: 10;
(3) and (3) transferring the hard carbon pretreatment substance into a reaction kettle with a polytetrafluoroethylene lining, setting the temperature to be 200-300 ℃, reacting for 24-48 h, and cooling to room temperature to obtain the hard carbon pretreatment liquid.
Step 2, preparing nano zirconium silicide:
(1) respectively placing superfine zirconium powder and micro silicon powder in a vacuum drying oven for drying treatment, then uniformly mixing, placing in a graphite furnace, heating to 900-1000 ℃ under the protection of inert gas atmosphere for preheating for 0.5-1 h, introducing hydrogen, gradually heating to 1200-1300 ℃ at the speed of 10 ℃/min, reacting for 5-10 h, and cooling to room temperature to obtain a zirconium silicide crude product;
wherein the mol ratio of the superfine zirconium powder to the micro silicon powder is 1: 2-3;
(2) adding the zirconium silicide crude product into ethanol, uniformly dispersing, performing ultrasonic treatment for 0.5-1 h, drying, grinding, and crushing in a nano-scale superfine crusher to obtain nano zirconium silicide with the particle size of 50-100 nm;
wherein the solid-to-liquid ratio of the zirconium silicide crude product to the ethanol is 1: 30.
Step 3, preparing modified nano zirconium silicide:
(1) weighing scandium chloride, mixing and dissolving with deionized water, adding nano zirconium silicide and a dispersing agent, dispersing uniformly, then dropwise adding a sodium hydroxide solution with the concentration of 0.1mol/L until the pH value of the liquid is 9-10, transferring the liquid to a reaction kettle with a polytetrafluoroethylene lining after dispersing uniformly, setting the temperature to be 150-220 ℃, reacting for 12-18 h, cooling to room temperature, washing for 3 times with acetone, then washing with deionized water to be neutral, and drying at 80-100 ℃ to obtain a modified zirconium silicide precursor;
wherein the solid-to-liquid ratio of scandium chloride to deionized water is 1: 20-30; the mass ratio of the polyethylene glycol to the deionized water is 1-5: 100; the mass ratio of the nano zirconium silicide to the scandium chloride is 8-10: 1;
(2) grinding the modified zirconium silicide precursor into powder, placing the powder in a graphite furnace, heating to 1000-1200 ℃, calcining for 10-12 h, cooling to room temperature, grinding, and placing the powder in a nano-scale superfine grinder for grinding to obtain the modified nano zirconium silicide with the particle size of 50-100 nm.
Step 4, preparing the hard carbon nano material:
(1) adding modified nano zirconium silicide into the hard carbon pretreatment liquid, uniformly dispersing, transferring into a reaction kettle with a polytetrafluoroethylene lining, heating to 200-250 ℃, reacting for 18-24 h, cooling to room temperature, filtering to obtain a solid, washing with acetone for 3 times, then washing with deionized water to be neutral, placing in an oven at 80-100 ℃, and drying for 12-20 h to obtain a hard carbon nano material precursor;
wherein the solid-to-liquid ratio of the modified nano zirconium silicide to the hard carbon pretreatment liquid is 1: 10-20;
(2) and (3) placing the precursor of the hard carbon nano material in a corundum crucible, then placing the crucible in a tubular resistance furnace, heating to 500-1000 ℃ at the speed of 5-10 ℃/min under the protection of nitrogen atmosphere, and pyrolyzing for 6-8 hours to obtain the hard carbon nano material.
Example 2
A preparation method of a hard carbon nano material for an ion battery comprises the following steps:
step 1, preparing a hard carbon pretreatment solution:
(1) washing loquat seeds, grinding the loquat seeds into powder, and sieving the powder to obtain loquat seed powder with the particle size of 150-300 mu m;
(2) adding loquat core powder into deionized water, uniformly dispersing, adding concentrated sulfuric acid with the mass concentration of 98%, and uniformly stirring to obtain a hard carbon pretreatment substance;
wherein the solid-to-liquid ratio of the loquat seed powder to the deionized water is 1: 20-30; the mass ratio of concentrated sulfuric acid to loquat core powder is 1-2: 10;
(3) and (3) transferring the hard carbon pretreatment substance into a reaction kettle with a polytetrafluoroethylene lining, setting the temperature to be 200-300 ℃, reacting for 24-48 h, and cooling to room temperature to obtain the hard carbon pretreatment liquid.
Step 2, preparing nano zirconium silicide:
(1) respectively placing superfine zirconium powder and micro silicon powder in a vacuum drying oven for drying treatment, then uniformly mixing, placing in a graphite furnace, heating to 900-1000 ℃ under the protection of inert gas atmosphere for preheating for 0.5-1 h, introducing hydrogen, gradually heating to 1200-1300 ℃ at the speed of 10 ℃/min, reacting for 5-10 h, and cooling to room temperature to obtain a zirconium silicide crude product;
wherein the mol ratio of the superfine zirconium powder to the micro silicon powder is 1: 2-3;
(2) adding the zirconium silicide crude product into ethanol, uniformly dispersing, performing ultrasonic treatment for 0.5-1 h, drying, grinding, and crushing in a nano-scale superfine crusher to obtain nano zirconium silicide with the particle size of 50-100 nm;
wherein the solid-to-liquid ratio of the zirconium silicide crude product to the ethanol is 1: 30.
Step 3, preparing modified nano zirconium silicide:
(1) weighing scandium chloride, mixing and dissolving with deionized water, adding nano zirconium silicide and a dispersing agent, dispersing uniformly, then dropwise adding a sodium hydroxide solution with the concentration of 0.1mol/L until the pH value of the liquid is 9-10, transferring the liquid to a reaction kettle with a polytetrafluoroethylene lining after dispersing uniformly, setting the temperature to be 150-220 ℃, reacting for 12-18 h, cooling to room temperature, washing for 3 times with acetone, then washing with deionized water to be neutral, and drying at 80-100 ℃ to obtain a modified zirconium silicide precursor;
wherein the solid-to-liquid ratio of scandium chloride to deionized water is 1: 20-30; the mass ratio of the polyethylene glycol to the deionized water is 1-5: 100; the mass ratio of the nano zirconium silicide to the scandium chloride is 8-10: 1;
(2) grinding the modified zirconium silicide precursor into powder, placing the powder in a graphite furnace, heating to 1000-1200 ℃, calcining for 10-12 h, cooling to room temperature, grinding, and placing the powder in a nano-scale superfine grinder for grinding to obtain the modified nano zirconium silicide with the particle size of 50-100 nm.
Step 4, preparing the hard carbon nano material:
(1) adding modified nano zirconium silicide into the hard carbon pretreatment liquid, uniformly dispersing, transferring into a reaction kettle with a polytetrafluoroethylene lining, heating to 200-250 ℃, reacting for 18-24 h, cooling to room temperature, filtering to obtain a solid, washing with acetone for 3 times, then washing with deionized water to be neutral, placing in an oven at 80-100 ℃, and drying for 12-20 h to obtain a hard carbon nano material precursor;
wherein the solid-to-liquid ratio of the modified nano zirconium silicide to the hard carbon pretreatment liquid is 1: 10-20;
(2) and (3) placing the precursor of the hard carbon nano material in a corundum crucible, then placing the crucible in a tubular resistance furnace, heating to 500-1000 ℃ at the speed of 5-10 ℃/min under the protection of nitrogen atmosphere, and pyrolyzing for 6-8 hours to obtain the hard carbon nano material.
Example 3
A preparation method of a hard carbon nano material for an ion battery comprises the following steps:
step 1, preparing a hard carbon pretreatment solution:
(1) cleaning the avocado kernels, grinding the avocado kernels into powder, and sieving the powder to obtain avocado kernel powder with the particle size of 150-300 microns;
(2) adding avocado kernel powder into deionized water, uniformly dispersing, adding concentrated sulfuric acid with the mass concentration of 98%, and uniformly stirring to obtain a hard carbon pretreatment substance;
wherein the solid-to-liquid ratio of the avocado kernel powder to the deionized water is 1: 20-30; the mass ratio of the concentrated sulfuric acid to the avocado kernel powder is 1-2: 10;
(3) and (3) transferring the hard carbon pretreatment substance into a reaction kettle with a polytetrafluoroethylene lining, setting the temperature to be 200-300 ℃, reacting for 24-48 h, and cooling to room temperature to obtain the hard carbon pretreatment liquid.
Step 2, preparing nano zirconium silicide:
(1) respectively placing superfine zirconium powder and micro silicon powder in a vacuum drying oven for drying treatment, then uniformly mixing, placing in a graphite furnace, heating to 900-1000 ℃ under the protection of inert gas atmosphere for preheating for 0.5-1 h, introducing hydrogen, gradually heating to 1200-1300 ℃ at the speed of 10 ℃/min, reacting for 5-10 h, and cooling to room temperature to obtain a zirconium silicide crude product;
wherein the mol ratio of the superfine zirconium powder to the micro silicon powder is 1: 2-3;
(2) adding the zirconium silicide crude product into ethanol, uniformly dispersing, performing ultrasonic treatment for 0.5-1 h, drying, grinding, and crushing in a nano-scale superfine crusher to obtain nano zirconium silicide with the particle size of 50-100 nm;
wherein the solid-to-liquid ratio of the zirconium silicide crude product to the ethanol is 1: 30.
Step 3, preparing modified nano zirconium silicide:
(1) weighing scandium chloride, mixing and dissolving with deionized water, adding nano zirconium silicide and a dispersing agent, dispersing uniformly, then dropwise adding a sodium hydroxide solution with the concentration of 0.1mol/L until the pH value of the liquid is 9-10, transferring the liquid to a reaction kettle with a polytetrafluoroethylene lining after dispersing uniformly, setting the temperature to be 150-220 ℃, reacting for 12-18 h, cooling to room temperature, washing for 3 times with acetone, then washing with deionized water to be neutral, and drying at 80-100 ℃ to obtain a modified zirconium silicide precursor;
wherein the solid-to-liquid ratio of scandium chloride to deionized water is 1: 20-30; the mass ratio of the polyethylene glycol to the deionized water is 1-5: 100; the mass ratio of the nano zirconium silicide to the scandium chloride is 8-10: 1;
(2) grinding the modified zirconium silicide precursor into powder, placing the powder in a graphite furnace, heating to 1000-1200 ℃, calcining for 10-12 h, cooling to room temperature, grinding, and placing the powder in a nano-scale superfine grinder for grinding to obtain the modified nano zirconium silicide with the particle size of 50-100 nm.
Step 4, preparing the hard carbon nano material:
(1) adding modified nano zirconium silicide into the hard carbon pretreatment liquid, uniformly dispersing, transferring into a reaction kettle with a polytetrafluoroethylene lining, heating to 200-250 ℃, reacting for 18-24 h, cooling to room temperature, filtering to obtain a solid, washing with acetone for 3 times, then washing with deionized water to be neutral, placing in an oven at 80-100 ℃, and drying for 12-20 h to obtain a hard carbon nano material precursor;
wherein the solid-to-liquid ratio of the modified nano zirconium silicide to the hard carbon pretreatment liquid is 1: 10-20;
(2) and (3) placing the precursor of the hard carbon nano material in a corundum crucible, then placing the crucible in a tubular resistance furnace, heating to 500-1000 ℃ at the speed of 5-10 ℃/min under the protection of nitrogen atmosphere, and pyrolyzing for 6-8 hours to obtain the hard carbon nano material.
Example 4
An application of the hard carbon nanomaterial prepared according to the method of embodiment 1 in a sodium ion battery is specifically as follows:
the process of preparing the negative electrode of the sodium ion battery using the hard carbon nanomaterial prepared by the method of example 1 is as follows: mixing the hard carbon nano material with polyvinylidene fluoride according to the mass ratio of 10:1, adding NMP (N-methyl pyrrolidone) to prepare slurry, coating the slurry on an aluminum foil, and drying to obtain the sodium-ion battery cathode.
Example 5
An application of the hard carbon nanomaterial prepared according to the method of embodiment 2 in a sodium ion battery is specifically as follows:
the process of preparing the negative electrode of the sodium ion battery using the hard carbon nanomaterial prepared by the method of example 2 is as follows: mixing the hard carbon nano material with polyvinylidene fluoride according to the mass ratio of 10:1, adding NMP (N-methyl pyrrolidone) to prepare slurry, coating the slurry on an aluminum foil, and drying to obtain the sodium-ion battery cathode.
Example 6
An application of the hard carbon nanomaterial prepared according to the method of embodiment 3 in a sodium ion battery is specifically as follows:
the process of preparing the negative electrode of the sodium ion battery using the hard carbon nanomaterial prepared by the method of example 3 is as follows: mixing the hard carbon nano material with polyvinylidene fluoride according to the mass ratio of 10:1, adding NMP (N-methyl pyrrolidone) to prepare slurry, coating the slurry on an aluminum foil, and drying to obtain the sodium-ion battery cathode.
Example 7
An application of the hard carbon nanomaterial prepared according to the method of embodiment 1 in a lithium ion battery specifically comprises:
the process of preparing the lithium ion battery negative electrode using the hard carbon nanomaterial prepared by the method of example 1 is as follows: mixing the hard carbon nano material with polytetrafluoroethylene according to the mass ratio of 10:1, adding NMP (N-methyl pyrrolidone) to prepare slurry, coating the slurry on copper foil, and drying to obtain the lithium ion battery cathode.
Example 8
An application of the hard carbon nanomaterial prepared according to the method of embodiment 2 in a lithium ion battery specifically comprises:
the process of preparing the lithium ion battery negative electrode using the hard carbon nanomaterial prepared by the method of example 2 is as follows: mixing the hard carbon nano material with polytetrafluoroethylene according to the mass ratio of 10:1, adding NMP (N-methyl pyrrolidone) to prepare slurry, coating the slurry on copper foil, and drying to obtain the lithium ion battery cathode.
Example 9
An application of the hard carbon nanomaterial prepared according to the method of embodiment 3 in a lithium ion battery specifically comprises:
the process of preparing the lithium ion battery negative electrode using the hard carbon nanomaterial prepared by the method of example 3 is as follows: mixing the hard carbon nano material with polytetrafluoroethylene according to the mass ratio of 10:1, adding NMP (N-methyl pyrrolidone) to prepare slurry, coating the slurry on copper foil, and drying to obtain the lithium ion battery cathode.
Comparative example 1
A preparation method of a hard carbon nano material for an ion battery comprises the following steps:
step 1, preparing a hard carbon pretreatment solution:
(1) cleaning mango seeds, grinding the mango seeds into powder, and sieving the powder to obtain mango seed powder with the particle size of 150-300 mu m;
(2) adding mango seed powder into deionized water, uniformly dispersing, adding concentrated sulfuric acid with the mass concentration of 98%, and uniformly stirring to obtain a hard carbon pretreatment substance;
wherein the solid-to-liquid ratio of the mango seed powder to the deionized water is 1: 20-30; the mass ratio of concentrated sulfuric acid to mango seed powder is 1-2: 10;
(3) and (3) transferring the hard carbon pretreatment substance into a reaction kettle with a polytetrafluoroethylene lining, setting the temperature to be 200-300 ℃, reacting for 24-48 h, and cooling to room temperature to obtain the hard carbon pretreatment liquid.
Step 2, preparing nano zirconium silicide:
(1) respectively placing superfine zirconium powder and micro silicon powder in a vacuum drying oven for drying treatment, then uniformly mixing, placing in a graphite furnace, heating to 900-1000 ℃ under the protection of inert gas atmosphere for preheating for 0.5-1 h, introducing hydrogen, gradually heating to 1200-1300 ℃ at the speed of 10 ℃/min, reacting for 5-10 h, and cooling to room temperature to obtain a zirconium silicide crude product;
wherein the mol ratio of the superfine zirconium powder to the micro silicon powder is 1: 2-3;
(2) adding the zirconium silicide crude product into ethanol, uniformly dispersing, performing ultrasonic treatment for 0.5-1 h, drying, grinding, and crushing in a nano-scale superfine crusher to obtain nano zirconium silicide with the particle size of 50-100 nm;
wherein the solid-to-liquid ratio of the zirconium silicide crude product to the ethanol is 1: 30.
Step 3, preparing the hard carbon nano material:
(1) adding nano zirconium silicide into the pretreatment liquid of hard carbon, uniformly dispersing, transferring into a reaction kettle with a polytetrafluoroethylene lining, heating to 200-250 ℃, reacting for 18-24 h, cooling to room temperature, filtering to obtain a solid, washing with acetone for 3 times, then washing with deionized water to be neutral, placing in an oven at 80-100 ℃, and drying for 12-20 h to obtain a precursor of a hard carbon nano material;
wherein the solid-to-liquid ratio of the nano zirconium silicide to the hard carbon pretreatment liquid is 1: 10-20;
(2) and (3) placing the precursor of the hard carbon nano material in a corundum crucible, then placing the crucible in a tubular resistance furnace, heating to 500-1000 ℃ at the speed of 5-10 ℃/min under the protection of nitrogen atmosphere, and pyrolyzing for 6-8 hours to obtain the hard carbon nano material.
An application of a hard carbon nano material in a sodium ion battery specifically comprises the following steps:
the process for preparing the cathode of the sodium ion battery by using the hard carbon nano material prepared by the method comprises the following steps: mixing the hard carbon nano material with polyvinylidene fluoride according to the mass ratio of 10:1, adding NMP (N-methyl pyrrolidone) to prepare slurry, coating the slurry on an aluminum foil, and drying to obtain the sodium-ion battery cathode.
Comparative example 2
A preparation method of a hard carbon nano material for an ion battery comprises the following steps:
step 1, preparing a hard carbon pretreatment solution:
(1) cleaning mango seeds, grinding the mango seeds into powder, and sieving the powder to obtain mango seed powder with the particle size of 150-300 mu m;
(2) adding mango seed powder into deionized water, uniformly dispersing, adding concentrated sulfuric acid with the mass concentration of 98%, and uniformly stirring to obtain a hard carbon pretreatment substance;
wherein the solid-to-liquid ratio of the mango seed powder to the deionized water is 1: 20-30; the mass ratio of concentrated sulfuric acid to mango seed powder is 1-2: 10;
(3) and (3) transferring the hard carbon pretreatment substance into a reaction kettle with a polytetrafluoroethylene lining, setting the temperature to be 200-300 ℃, reacting for 24-48 h, and cooling to room temperature to obtain the hard carbon pretreatment liquid.
Step 2, preparing nano zirconium silicide:
(1) respectively placing superfine zirconium powder and micro silicon powder in a vacuum drying oven for drying treatment, then uniformly mixing, placing in a graphite furnace, heating to 900-1000 ℃ under the protection of inert gas atmosphere for preheating for 0.5-1 h, introducing hydrogen, gradually heating to 1200-1300 ℃ at the speed of 10 ℃/min, reacting for 5-10 h, and cooling to room temperature to obtain a zirconium silicide crude product;
wherein the mol ratio of the superfine zirconium powder to the micro silicon powder is 1: 2-3;
(2) adding the zirconium silicide crude product into ethanol, uniformly dispersing, performing ultrasonic treatment for 0.5-1 h, drying, grinding, and crushing in a nano-scale superfine crusher to obtain nano zirconium silicide with the particle size of 50-100 nm;
wherein the solid-to-liquid ratio of the zirconium silicide crude product to the ethanol is 1: 30.
Step 3, preparing the hard carbon nano material:
(1) adding nano zirconium silicide into the pretreatment liquid of hard carbon, uniformly dispersing, transferring into a reaction kettle with a polytetrafluoroethylene lining, heating to 200-250 ℃, reacting for 18-24 h, cooling to room temperature, filtering to obtain a solid, washing with acetone for 3 times, then washing with deionized water to be neutral, placing in an oven at 80-100 ℃, and drying for 12-20 h to obtain a precursor of a hard carbon nano material;
wherein the solid-to-liquid ratio of the nano zirconium silicide to the hard carbon pretreatment liquid is 1: 10-20;
(2) and (3) placing the precursor of the hard carbon nano material in a corundum crucible, then placing the crucible in a tubular resistance furnace, heating to 500-1000 ℃ at the speed of 5-10 ℃/min under the protection of nitrogen atmosphere, and pyrolyzing for 6-8 hours to obtain the hard carbon nano material.
An application of a hard carbon nano material in a lithium ion battery specifically comprises the following steps:
the process for preparing the lithium ion battery cathode by using the hard carbon nano material prepared by the method comprises the following steps: mixing the hard carbon nano material with polytetrafluoroethylene according to the mass ratio of 10:1, adding NMP (N-methyl pyrrolidone) to prepare slurry, coating the slurry on copper foil, and drying to obtain the lithium ion battery cathode.
Comparative example 3
A preparation method of a hard carbon nano material for an ion battery comprises the following steps:
step 1, preparing a hard carbon pretreatment solution:
(1) cleaning mango seeds, grinding the mango seeds into powder, and sieving the powder to obtain mango seed powder with the particle size of 150-300 mu m;
(2) adding the mango seed powder into deionized water, uniformly dispersing, adding concentrated sulfuric acid with the mass concentration of 98%, and uniformly stirring to obtain a hard carbon pretreatment substance;
wherein the solid-to-liquid ratio of the mango seed powder to the deionized water is 1: 20-30; the mass ratio of concentrated sulfuric acid to mango seed powder is 1-2: 10;
(3) transferring the hard carbon pretreatment substance into a reaction kettle with a polytetrafluoroethylene lining, setting the temperature to be 200-300 ℃, reacting for 24-48 h, cooling to room temperature, filtering to obtain a solid, washing for 3 times by using acetone, then washing to be neutral by using deionized water, placing in an oven at 80-100 ℃, and drying for 12-20 h to obtain a hard carbon nano material precursor;
(4) and (3) placing the precursor of the hard carbon nano material in a corundum crucible, then placing the crucible in a tubular resistance furnace, heating to 500-1000 ℃ at the speed of 5-10 ℃/min under the protection of nitrogen atmosphere, and pyrolyzing for 6-8 hours to obtain the hard carbon nano material.
An application of a hard carbon nano material in a lithium ion battery specifically comprises the following steps:
the process for preparing the lithium ion battery cathode by using the hard carbon nano material prepared by the method comprises the following steps: mixing the hard carbon nano material with polyvinylidene fluoride according to the mass ratio of 10:1, adding NMP (N-methyl pyrrolidone) to prepare slurry, coating the slurry on copper foil, and drying to obtain the lithium ion battery cathode.
In order to more clearly illustrate the present invention, performance tests were performed on the negative electrodes of the batteries prepared in examples 4 to 9 of the present invention and comparative examples 1 to 3.
Specifically, the results of the charge and discharge tests of the negative electrodes of the batteries prepared in examples 4 to 9 of the present invention and comparative examples 1 to 3 were performed at 0.1C charge and discharge rate, respectively, and are shown in table 1.
Wherein, the first charge-discharge efficiency is equal to the first lithium removal specific capacity/the first lithium insertion specific capacity multiplied by 100 percent;
after 50 cycles, the capacity retention rate is equal to the lithium removal specific capacity/first lithium removal specific capacity multiplied by 100 percent after 50 cycles.
TABLE 1 Charge/discharge test results
As can be seen from table 1, the first charge-discharge efficiency of the sodium ion battery negative electrodes prepared in embodiments 4 to 6 of the present invention can reach over 86%, and the capacity retention rate after 500 cycles can also reach over 84%; the first charge-discharge efficiency of the lithium ion battery cathode prepared in the embodiments 7-9 can reach more than 90%, and the capacity retention rate after 500 cycles can also reach more than 85%; in the comparative example 2, the hard carbon material added with the nano zirconium silicide is used as the cathode of the lithium ion battery, the first charge-discharge efficiency can reach 75%, and the capacity retention rate after 500 cycles can also reach 82%; in the comparative example 1 of the invention, the hard carbon material added with the nano zirconium silicide is used as the cathode of the sodium ion battery, the first charge-discharge efficiency can reach 72%, and the capacity retention rate after 500 cycles can also reach 81%; in contrast, in comparative example 3, the hard carbon material prepared by using only the biomass material as the negative electrode of the lithium ion battery has a first charge-discharge efficiency of only 54% and a capacity retention rate after 500 cycles of only 70%. The data prove that the hard carbon nano material prepared in the embodiments 1 to 3 is very suitable for being used as a negative electrode material of a lithium/sodium ion battery.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of a hard carbon nano material for an ion battery is characterized by comprising the following steps:
step 1, preparing a hard carbon pretreatment solution:
crushing fruit kernels, mixing the crushed fruit kernels with deionized water, and adding concentrated sulfuric acid for carbonization treatment to obtain hard carbon pretreatment liquid;
step 2, preparing nano zirconium silicide:
preparing nano zirconium silicide by using superfine zirconium powder and micro silicon powder;
step 3, preparing modified nano zirconium silicide:
scandium chloride is used for modifying the nano zirconium silicide to obtain modified nano zirconium silicide;
step 4, preparing the hard carbon nano material:
and reacting the modified nano zirconium silicide with the hard carbon pretreatment solution, and pyrolyzing to obtain the hard carbon nano material.
2. The method for preparing the hard carbon nanomaterial for the ion battery according to claim 1, wherein the step 1 specifically comprises:
step 1, preparing a hard carbon pretreatment solution:
(1) cleaning fruit kernels, and grinding the fruit kernels into powder to obtain fruit kernel powder;
(2) adding the fruit kernel powder into deionized water, uniformly dispersing, adding concentrated sulfuric acid with the mass concentration of 98%, and uniformly stirring to obtain a hard carbon pretreatment substance;
wherein the solid-to-liquid ratio of the fruit stone powder to the deionized water is 1: 20-30; the mass ratio of concentrated sulfuric acid to fruit kernel powder is 1-2: 10; the solid-liquid ratio is a mass-volume ratio;
(3) and (3) transferring the hard carbon pretreatment substance into a reaction kettle with a polytetrafluoroethylene lining, setting the temperature to be 200-300 ℃, reacting for 24-48 h, and cooling to room temperature to obtain a hard carbon pretreatment liquid.
3. The method for preparing the hard carbon nanomaterial for the ion battery according to claim 1, wherein the step 2 specifically comprises:
step 2, preparing nano zirconium silicide:
(1) respectively placing superfine zirconium powder and micro silicon powder in a vacuum drying oven for drying treatment, then uniformly mixing, placing in a graphite furnace, heating to 900-1000 ℃ under the protection of inert gas atmosphere for preheating for 0.5-1 h, introducing hydrogen, gradually heating to 1200-1300 ℃ at the speed of 10 ℃/min, reacting for 5-10 h, and cooling to room temperature to obtain a zirconium silicide crude product;
wherein the mol ratio of the superfine zirconium powder to the micro silicon powder is 1: 2-3;
(2) and adding the zirconium silicide crude product into ethanol, uniformly dispersing, performing ultrasonic treatment for 0.5-1 h, drying, grinding, and crushing in a nano-scale superfine crusher to obtain the nano-zirconium silicide.
4. The method for preparing the hard carbon nanomaterial for the ion battery according to claim 1, wherein the step 3 specifically comprises:
step 3, preparing modified nano zirconium silicide:
(1) weighing scandium chloride, mixing and dissolving with deionized water, adding nano zirconium silicide and a dispersing agent, dispersing uniformly, then dropwise adding a sodium hydroxide solution with the concentration of 0.1mol/L until the pH value of the liquid is 9-10, transferring the liquid to a reaction kettle with a polytetrafluoroethylene lining after dispersing uniformly, setting the temperature to be 150-220 ℃, reacting for 12-18 h, cooling to room temperature, washing for 3 times with acetone, then washing with deionized water to be neutral, and drying at 80-100 ℃ to obtain a modified zirconium silicide precursor;
wherein the solid-to-liquid ratio of scandium chloride to deionized water is 1: 20-30; the mass ratio of the polyethylene glycol to the deionized water is 1-5: 100; the mass ratio of the nano zirconium silicide to the scandium chloride is 8-10: 1; the solid-liquid ratio is a mass-volume ratio;
(2) grinding the modified zirconium silicide precursor into powder, placing the powder in a graphite furnace, heating to 1000-1200 ℃, calcining for 10-12 h, cooling to room temperature, grinding, and placing the powder in a nano-scale superfine crusher for crushing to obtain the modified nano-zirconium silicide.
5. The method for preparing the hard carbon nanomaterial for the ion battery according to claim 1, wherein the step 4 specifically comprises:
step 4, preparing the hard carbon nano material:
(1) adding modified nano zirconium silicide into the hard carbon pretreatment liquid, uniformly dispersing, transferring into a reaction kettle with a polytetrafluoroethylene lining, heating to 200-250 ℃, reacting for 18-24 h, cooling to room temperature, filtering to obtain a solid, washing with acetone for 3 times, then washing with deionized water to be neutral, placing in an oven at 80-100 ℃, and drying for 12-20 h to obtain a hard carbon nano material precursor;
wherein the solid-to-liquid ratio of the modified nano zirconium silicide to the hard carbon pretreatment liquid is 1: 10-20; the solid-liquid ratio is a mass-volume ratio;
(2) and (3) placing the precursor of the hard carbon nano material in a corundum crucible, placing the crucible in a tubular resistance furnace, heating to 500-600 ℃ at the speed of 2-5 ℃/min under the protection of nitrogen atmosphere, and pyrolyzing for 6-8 hours to obtain the hard carbon nano material.
6. The method for preparing a hard carbon nanomaterial for an ion battery according to claim 1, wherein the fruit core is one or more of mango, loquat and shea nut cores.
7. The method for preparing a hard carbon nanomaterial for an ion battery according to claim 2, wherein the particle size of the fruit kernel powder is 150-300 μm.
8. The method for preparing the hard carbon nanomaterial for the ion battery according to claim 3, wherein in the step 2, the solid-to-liquid ratio of the zirconium silicide crude product to ethanol is 1: 20-50; the solid-liquid ratio is a mass-volume ratio.
9. An application of a hard carbon nano material for an ion battery in a sodium ion battery is characterized in that the hard carbon nano material is prepared by the preparation method of the hard carbon nano material for the ion battery according to any one of claims 1 to 8.
10. An application of a hard carbon nano material for an ion battery in a lithium ion battery is characterized in that the hard carbon nano material is prepared by the preparation method of the hard carbon nano material for the ion battery according to any one of claims 1 to 8.
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