CN104701498A - Method for preparing biochar/ammonium vanadate lithium ion cell cathode material - Google Patents
Method for preparing biochar/ammonium vanadate lithium ion cell cathode material Download PDFInfo
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Abstract
The invention discloses a method for preparing a biochar/ammonium vanadate lithium ion cell cathode material. The method comprises the steps of cleaning and cutting a biomass preformed body into pieces, drying the biomass preformed body, and adding concentrated nitric acid for homogeneous reaction, so that a reaction product is obtained; conducting suction filtration and drying on the reaction product, and carbonizing the reaction product in a tubular atmosphere oven, so that a carbonized product is obtained; conducting washing and suction filtration on the carbonized product, and drying the carbonized product, so that porous biochar is obtained; finally, adding biochar into a NH4VO3 solution obtained from deionized water by means of ammonium metavanadate, and placing the mixture in a hydrothermal induction heater, so that the biochar/ammonium vanadate lithium ion cell cathode material is obtained. The obtained biochar/ammonium vanadate composite material has excellent conductivity, and specific capacity and stability are also improved remarkably. The preparing method is simple, reaction temperature is low, reaction time is short, subsequent processing is not needed, environmental friendliness is realized, and large-scale production can be achieved with the method.
Description
Technical field
The invention belongs to anode material for lithium-ion batteries preparation field, be specifically related to the preparation method of a kind of biological carbon/ammonium vanadate anode material for lithium-ion batteries.
Background technology
Oxyvanadium compound and vanadate intercalation materials of li ions are due to relative inexpensiveness, and synthetic method is simple, and specific capacity high becomes the focus of Recent study.Ammonium vanadate nano material, as the important vanadate of a class, has the layer structure that vanadium oxygen polyhedron is formed, wherein, and NH
4+be positioned at the interlayer that vanadium oxygen polyhedron is formed, make it have the open architecture that can embed metal ion and the characteristic that thermal induced phase transition occurs.Therefore, ammonium vanadate has good conductivity performance usually, and has higher theoretical specific capacity, is expected to become the novel lithium ion battery electrode material of a class.
Current preparation NH
4v
3o
8method mainly contain: the precipitation method and hydro thermal method.Wherein, hydro thermal method is a kind of effectively route of synthesis.The pattern of synthesis also has shuttle shape, flower-shaped and banded etc.But precipitation method synthesis NH
4v
3o
8have that course of reaction is wayward, shortcoming, the water heat transfer NH such as have side reaction generation, product purity low
4v
3o
8there is the shortcomings such as reaction temperature is relatively high, the reaction time is longer.And ammonium vanadate is little due to itself conductivity, cause its conductivity poor.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of biological carbon/ammonium vanadate anode material for lithium-ion batteries, to overcome the defect that above-mentioned prior art exists, can prepare that electric conductivity excellence, specific capacity are high by preparation method of the present invention, stable cycle performance and life-span long biological carbon/vanadic acid ammonia composite material.
For achieving the above object, the present invention adopts following technical scheme:
A preparation method for biological carbon/ammonium vanadate anode material for lithium-ion batteries, comprises the following steps:
(1) biomass precast body is cleaned removing surface impurity, shred to obtain homogeneous bulky A;
(2) block B is obtained by dry for homogeneous bulky A;
(3) carry out homogeneous reaction after adding red fuming nitric acid (RFNA) in block B, obtain product C;
(4) carry out carbonization after being dried by product C suction filtration, obtain carbonized product D;
(5) carbonized product D is added alcohol immersion, then with suction filtration after distilled water and ethanol washing, then dry, obtain the charcoal E of loose structure;
(6) be dissolved in deionized water by ammonium metavanadate, obtained concentration is the NH of 0.10 ~ 0.30mol/L
4vO
3solution F;
(7) by NH
4vO
3the pH value of solution F is adjusted to 0.5 ~ 2.0, to NH
4vO
3the mass ratio being 1:10 ~ 1:20 according to E:F in solution F adds biological carbon E, again the mixture obtained is proceeded in reactor, after reactor is sealed, be placed in hydro-thermal induction heating instrument, with the induction frequencies of 400 ~ 800KHz by room temperature to 160 ~ 220 DEG C, and be incubated 10 ~ 30min, be then cooled to 60 ~ 80 DEG C, insulation 10 ~ 20min, obtains suspension;
(8) suspension centrifugation is obtained powder product, then powder product is used respectively deionized water and soaked in absolute ethyl alcohol and washing, then dry, grinding, obtains NH
4v
3o
8/ C nano compound.
Further, in step (1), biomass precast body is the one in banana skin, shrimp shell, Chinese parasol leaf, wheat stalk or maize straw.
Further, in step (1), the size dimension of homogeneous bulky A is 4 ~ 6mm.
Further, in step (2) by homogeneous bulky A at room temperature dry 0.5 ~ 1h obtain block B.
Further, in step (3), the concentration of red fuming nitric acid (RFNA) is 2 ~ 5molL
-1.
Further, in step (3), the condition of homogeneous reaction is: be incubated 20 ~ 50min after being warming up to 150 DEG C ~ 180 DEG C with the heating rate of 15 DEG C/min, then naturally cool to room temperature.
Further, carbonization in tube-type atmosphere furnace is moved into after being dried by product C suction filtration in step (4), described tube-type atmosphere furnace passes into nitrogen, the condition of carbonization is: tube-type atmosphere furnace is warmed up to 50 DEG C by 10min, after 75min is warmed up to 600 ~ 800 DEG C, and be incubated 60 ~ 180min at this temperature.
Further, in step (8) by powder product by the detailed process of deionized water and soaked in absolute ethyl alcohol and washing be respectively: powder product is first soaked 10 ~ 20min with deionized water, then deionized water is spent 5 ~ 10 times, use soaked in absolute ethyl alcohol 10 ~ 20min again, then use absolute ethanol washing 5 ~ 10 times.
Further, the baking temperature in step (8) is 80 ~ 110 DEG C, and the time is 6 ~ 8h.
A preparation method for biological carbon/ammonium vanadate anode material for lithium-ion batteries, comprises the following steps:
(1) Chinese parasol leaf is cleaned remove surface impurity, shred size dimension is the homogeneous bulky A of 4mm;
(2) by homogeneous bulky A at room temperature dry 0.5h obtain block B;
(3) in block B, adding concentration is 2molL
-1red fuming nitric acid (RFNA) after, be incubated 20min after being warming up to 150 DEG C with the heating rate of 15 DEG C/min, then naturally cool to room temperature, obtain product C;
(4) move in tube-type atmosphere furnace after being dried by product C suction filtration and carry out carbonization, tube-type atmosphere furnace is full of nitrogen, and the condition of carbonization is: tube-type atmosphere furnace is warmed up to 50 DEG C by 10min, and 75min is incubated 180min after being warmed up to 600 DEG C, obtains carbonized product D;
(5) carbonized product D is added alcohol immersion, then with distilled water wash wash three times with ethanol again three times after suction filtration, then dry, obtain the charcoal E of loose structure;
(6) be dissolved in deionized water by ammonium metavanadate, obtained concentration is the NH of 0.20mol/L
4vO
3solution F;
(7) by NH
4vO
3the pH value of solution F is adjusted to 0.5, to NH
4vO
3the mass ratio being 1:10 according to E:F in solution F adds biological carbon E, again the mixture obtained is proceeded in reactor, after reactor is sealed, be placed in hydro-thermal induction heating instrument, with the induction frequencies of 400KHz by room temperature to 160 DEG C, and be incubated 10min, be then cooled to 60 DEG C, insulation 10min, obtains suspension;
(8) suspension centrifugation is obtained powder product, powder product is first soaked 10min with deionized water, then deionized water is spent 5 times, use soaked in absolute ethyl alcohol 10min again, then absolute ethanol washing is used 5 times, then dry 6h at the temperature of 80 DEG C, more dried solid product is ground, obtain the NH of porous flake
4v
3o
8/ C nano compound, is biological carbon/ammonium vanadate anode material for lithium-ion batteries.
Compared with prior art, the present invention has following useful technique effect:
Biomass precast body of the present invention obtains charcoal, charcoal and ammonium metavanadate is adopted to prepare biological carbon/ammonium vanadate anode material for lithium-ion batteries, because biological carbon has larger interlamellar spacing, not only can provide condition for the fast transport of lithium ion, increase the capacity of material, can also intramolecular hydrogen bond be formed, the structure of stabilizing material, and then the cyclical stability that can improve material.Charcoal is the ordered porous shape material of short texture in addition, has larger specific area, effectively can increase the contact area of electrode material and electrolyte, and then significantly can improve the conductivity of material.Together with specific capacity high to the conductivity of biological carbon excellence and vanadic acid ammonia has organically been compounded in by the present invention, prepare biological carbon/ammonium vanadate composite material, by the biological carbon turned waste into wealth with there is height ratio capacity/ammonium vanadate material carried out compound, migration for electronics provides good passage, add the migration velocity of electronics, improve the conductivity of material, fast charging and discharging can be realized better.The present invention selects to have hydro-thermal actinobolia synthesising biological carbon/ammonium vanadate composite material that synthesis temperature is low, the cycle is short, obtained biological carbon/ammonium vanadate composite material, there is excellent electric conductivity (conductance making ammonium vanadate original obtains the lifting of the order of magnitude), and specific capacity (specific capacity of original for ammonium vanadate 260mAh/g is risen to 350mAh/g) have also been obtained and significantly improves, preparation method of the present invention is simple, reaction temperature is low, reaction time is short, and without the need to subsequent treatment, environmentally friendly, can large-scale production be applicable to.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of anode material for lithium-ion batteries prepared by the embodiment of the present invention 1;
Fig. 2 is ESEM (SEM) photo of the biological carbon that the embodiment of the present invention 1 step (5) obtains;
Fig. 3 is ESEM (SEM) photo of anode material for lithium-ion batteries prepared by the embodiment of the present invention 1.
Embodiment
Below embodiments of the present invention are described in further detail:
A preparation method for biological carbon/ammonium vanadate anode material for lithium-ion batteries, comprises the following steps:
(1) biomass precast body (biomass precast body is the one in banana skin, shrimp shell, Chinese parasol leaf, wheat stalk or maize straw) is cleaned remove surface impurity, shred size dimension is the homogeneous bulky A of 4 ~ 6mm;
(2) by homogeneous bulky A at room temperature dry 0.5 ~ 1h obtain block B;
(3) in block B, adding concentration is 2 ~ 5molL
-1red fuming nitric acid (RFNA) after carry out homogeneous reaction, the condition of homogeneous reaction is: after being warming up to 150 DEG C ~ 180 DEG C with the heating rate of 15 DEG C/min be incubated 20 ~ 50min, then naturally cool to room temperature, obtain product C;
(4) move in tube-type atmosphere furnace after product C suction filtration being dried and carry out carbonization, tube-type atmosphere furnace passes into nitrogen, the condition of carbonization is: tube-type atmosphere furnace is warmed up to 50 DEG C by 10min, is incubated 60 ~ 180min, obtains carbonized product D after 75min is warmed up to 600 ~ 800 DEG C;
(5) carbonized product D is added alcohol immersion, then with distilled water wash wash three times with ethanol again three times after suction filtration, then dry, obtain the charcoal E of loose structure;
(6) be dissolved in deionized water by ammonium metavanadate, obtained concentration is the NH of 0.10 ~ 0.30mol/L
4vO
3solution F;
(7) by NH
4vO
3the pH value of solution F is adjusted to 0.5 ~ 2.0, to NH
4vO
3the mass ratio being 1:10 ~ 1:20 according to E:F in solution F adds biological carbon E, again the mixture obtained is proceeded in reactor, after reactor is sealed, be placed in hydro-thermal induction heating instrument, with the induction frequencies of 400 ~ 800KHz by room temperature to 160 ~ 220 DEG C, and be incubated 10 ~ 30min, be then cooled to 60 ~ 80 DEG C, insulation 10 ~ 20min, obtains suspension;
(8) suspension centrifugation is obtained powder product, powder product is first soaked 10 ~ 20min with deionized water, then deionized water is spent 5 ~ 10 times, use soaked in absolute ethyl alcohol 10 ~ 20min again, then absolute ethanol washing 5 ~ 10 times, then dry 6 ~ 8h at the temperature of 80 ~ 110 DEG C, more dried solid product is ground, obtain the NH of porous flake or nano bar-shape
4v
3o
8/ C nano compound, is biological carbon/ammonium vanadate anode material for lithium-ion batteries.
Below in conjunction with embodiment, the present invention is described in further detail:
Embodiment 1
(1) Chinese parasol leaf is cleaned remove surface impurity, shred size dimension is the homogeneous bulky A of 4mm;
(2) by homogeneous bulky A at room temperature dry 0.5h obtain block B;
(3) in block B, adding concentration is 2molL
-1red fuming nitric acid (RFNA) after, be incubated 20min after being warming up to 150 DEG C with the heating rate of 15 DEG C/min, then naturally cool to room temperature, obtain product C;
(4) move in tube-type atmosphere furnace after being dried by product C suction filtration and carry out carbonization, tube-type atmosphere furnace passes into nitrogen, and the condition of carbonization is: tube-type atmosphere furnace is warmed up to 50 DEG C by 10min, and 75min is incubated 180min after being warmed up to 600 DEG C, obtains carbonized product D;
(5) carbonized product D is added alcohol immersion, then wash three times with distilled water and wash three rear suction filtrations with ethanol again, then dry, obtain the charcoal E of loose structure;
(6) be dissolved in deionized water by ammonium metavanadate, obtained concentration is the NH of 0.20mol/L
4vO
3solution F;
(7) by NH
4vO
3the pH value of solution F is adjusted to 0.5, to NH
4vO
3the mass ratio being 1:10 according to E:F in solution F adds biological carbon E, again the mixture obtained is proceeded in reactor, after reactor is sealed, be placed in hydro-thermal induction heating instrument, with the induction frequencies of 400KHz by room temperature to 160 DEG C, and be incubated 10min, be then cooled to 60 DEG C, insulation 10min, obtains suspension;
(8) suspension centrifugation is obtained powder product, powder product is first soaked 10min with deionized water, then deionized water is spent 5 times, use soaked in absolute ethyl alcohol 10min again, then absolute ethanol washing is used 5 times, then dry 6h at the temperature of 80 DEG C, more dried solid product is ground, obtain the NH of porous flake
4v
3o
8/ C nano compound, is biological carbon/ammonium vanadate anode material for lithium-ion batteries.
As can be seen from Figure 1, positive electrode good crystallinity prepared by the present embodiment, purity is higher; As can be seen from Figure 2, in step (5), the charcoal E of preparation is porous flake; As can be seen from Figure 3, charcoal/ammonium vanadate positive electrode that prepared by the present embodiment is porous flake.
Embodiment 2
(1) wheat stalk is cleaned remove surface impurity, shred size dimension is the homogeneous bulky A of 6mm;
(2) by homogeneous bulky A at room temperature dry 1h obtain block B;
(3) in block B, adding concentration is 5molL
-1red fuming nitric acid (RFNA) after, be incubated 50min after being warming up to 180 DEG C with the heating rate of 15 DEG C/min, then naturally cool to room temperature, obtain product C;
(4) move in tube-type atmosphere furnace after being dried by product C suction filtration and carry out carbonization, tube-type atmosphere furnace passes into nitrogen, and the condition of carbonization is: tube-type atmosphere furnace is warmed up to 50 DEG C by 10min, and 75min is incubated 60min after being warmed up to 800 DEG C, obtains carbonized product D;
(5) carbonized product D added alcohol immersion, then wash three times with distilled water and wash suction filtrations after three times with ethanol again, then dry, obtain the charcoal E of loose structure;
(6) be dissolved in deionized water by ammonium metavanadate, obtained concentration is the NH of 0.10mol/L
4vO
3solution F;
(7) by NH
4vO
3the pH value of solution F is adjusted to 2.0, to NH
4vO
3the mass ratio being 1:20 according to E:F in solution F adds biological carbon E, again the mixture obtained is proceeded in reactor, after reactor is sealed, be placed in hydro-thermal induction heating instrument, with the induction frequencies of 800KHz by room temperature to 220 DEG C, and be incubated 30min, be then cooled to 80 DEG C, insulation 20min, obtains suspension;
(8) suspension centrifugation is obtained powder product, powder product is first soaked 20min with deionized water, then deionized water is spent 10 times, use soaked in absolute ethyl alcohol 20min again, then absolute ethanol washing is used 10 times, then dry 8h at the temperature of 110 DEG C, more dried solid product is ground, obtain the NH of porous flake
4v
3o
8/ C nano compound, is biological carbon/ammonium vanadate anode material for lithium-ion batteries.
Embodiment 3
(1) maize straw is cleaned remove surface impurity, shred size dimension is the homogeneous bulky A of 5mm;
(2) by homogeneous bulky A at room temperature dry 0.6h obtain block B;
(3) in block B, adding concentration is 4molL
-1red fuming nitric acid (RFNA) after, be incubated 30min after being warming up to 160 DEG C with the heating rate of 15 DEG C/min, then naturally cool to room temperature, obtain product C;
(4) move in tube-type atmosphere furnace after being dried by product C suction filtration and carry out carbonization, tube-type atmosphere furnace passes into nitrogen, and the condition of carbonization is: tube-type atmosphere furnace is warmed up to 50 DEG C by 10min, and 75min is incubated 100min after being warmed up to 700 DEG C, obtains carbonized product D;
(5) carbonized product D is added alcohol immersion, then wash three times with distilled water and wash three rear suction filtrations with ethanol again, then dry, obtain the charcoal E of loose structure;
(6) be dissolved in deionized water by ammonium metavanadate, obtained concentration is the NH of 0.30mol/L
4vO
3solution F;
(7) by NH
4vO
3the pH value of solution F is adjusted to 1.0, to NH
4vO
3the mass ratio being 1:15 according to E:F in solution F adds biological carbon E, again the mixture obtained is proceeded in reactor, after reactor is sealed, be placed in hydro-thermal induction heating instrument, with the induction frequencies of 500KHz by room temperature to 170 DEG C, and be incubated 15min, be then cooled to 65 DEG C, insulation 15min, obtains suspension;
(8) suspension centrifugation is obtained powder product, powder product is first soaked 15min with deionized water, then deionized water is spent 8 times, use soaked in absolute ethyl alcohol 15min again, then absolute ethanol washing is used 8 times, then dry 7h at the temperature of 100 DEG C, more dried solid product is ground, obtain the NH of porous flake
4v
3o
8/ C nano compound, is biological carbon/ammonium vanadate anode material for lithium-ion batteries.
Embodiment 4
(1) banana skin is cleaned remove surface impurity, shred size dimension is the homogeneous bulky A of 5mm;
(2) by homogeneous bulky A at room temperature dry 0.5h obtain block B;
(3) in block B, adding concentration is 3molL
-1red fuming nitric acid (RFNA) after, be incubated 40min after being warming up to 170 DEG C with the heating rate of 15 DEG C/min, then naturally cool to room temperature, obtain product C;
(4) move in tube-type atmosphere furnace after being dried by product C suction filtration and carry out carbonization, tube-type atmosphere furnace passes into nitrogen, and the condition of carbonization is: tube-type atmosphere furnace is warmed up to 50 DEG C by 10min, and 75min is incubated 150min after being warmed up to 600 DEG C, obtains carbonized product D;
(5) carbonized product D is added alcohol immersion, then with distilled water wash wash three times with ethanol again three times after suction filtration, then dry, obtain the charcoal E of loose structure;
(6) be dissolved in deionized water by ammonium metavanadate, obtained concentration is the NH of 0.20mol/L
4vO
3solution F;
(7) by NH
4vO
3the pH value of solution F is adjusted to 1.5, to NH
4vO
3the mass ratio being 1:10 according to E:F in solution F adds biological carbon E, again the mixture obtained is proceeded in reactor, after reactor is sealed, be placed in hydro-thermal induction heating instrument, with the induction frequencies of 600KHz by room temperature to 180 DEG C, and be incubated 25min, be then cooled to 70 DEG C, insulation 10min, obtains suspension;
(8) suspension centrifugation is obtained powder product, powder product is first soaked 10min with deionized water, then deionized water is spent 5 times, use soaked in absolute ethyl alcohol 15min again, then absolute ethanol washing is used 8 times, then dry 7h at the temperature of 90 DEG C, more dried solid product is ground, obtain the NH of nano bar-shape
4v
3o
8/ C nano compound, is biological carbon/ammonium vanadate anode material for lithium-ion batteries.
Embodiment 5
(1) shrimp shell is cleaned remove surface impurity, shred size dimension is the homogeneous bulky A of 6mm;
(2) by homogeneous bulky A at room temperature dry 1h obtain block B;
(3) in block B, adding concentration is 2molL
-1red fuming nitric acid (RFNA) after, be incubated 50min after being warming up to 180 DEG C with the heating rate of 15 DEG C/min, then naturally cool to room temperature, obtain product C;
(4) move in tube-type atmosphere furnace after being dried by product C suction filtration and carry out carbonization, tube-type atmosphere furnace passes into nitrogen, and the condition of carbonization is: tube-type atmosphere furnace is warmed up to 50 DEG C by 10min, and 75min is incubated 80min after being warmed up to 800 DEG C, obtains carbonized product D;
(5) carbonized product D is added alcohol immersion, then with distilled water wash wash three times with ethanol again three times after suction filtration, then dry, obtain the charcoal E of loose structure;
(6) be dissolved in deionized water by ammonium metavanadate, obtained concentration is the NH of 0.30mol/L
4vO
3solution F;
(7) by NH
4vO
3the pH value of solution F is adjusted to 2.0, to NH
4vO
3the mass ratio being 1:20 according to E:F in solution F adds biological carbon E, again the mixture obtained is proceeded in reactor, after reactor is sealed, be placed in hydro-thermal induction heating instrument, with the induction frequencies of 700KHz by room temperature to 220 DEG C, and be incubated 30min, be then cooled to 80 DEG C, insulation 20min, obtains suspension;
(8) suspension centrifugation is obtained powder product, powder product is first soaked 20min with deionized water, then deionized water is spent 10 times, use soaked in absolute ethyl alcohol 10min again, then absolute ethanol washing is used 5 times, then dry 6h at the temperature of 110 DEG C, more dried solid product is ground, obtain the NH of nano bar-shape
4v
3o
8/ C nano compound, is biological carbon/ammonium vanadate anode material for lithium-ion batteries.
Claims (10)
1. a preparation method for biological carbon/ammonium vanadate anode material for lithium-ion batteries, is characterized in that, comprise the following steps:
(1) biomass precast body is cleaned removing surface impurity, shred to obtain homogeneous bulky A;
(2) block B is obtained by dry for homogeneous bulky A;
(3) carry out homogeneous reaction after adding red fuming nitric acid (RFNA) in block B, obtain product C;
(4) carry out carbonization after being dried by product C suction filtration, obtain carbonized product D;
(5) carbonized product D is added alcohol immersion, then with suction filtration after distilled water and ethanol washing, then dry, obtain the charcoal E of loose structure;
(6) be dissolved in deionized water by ammonium metavanadate, obtained concentration is the NH of 0.10 ~ 0.30mol/L
4vO
3solution F;
(7) by NH
4vO
3the pH value of solution F is adjusted to 0.5 ~ 2.0, to NH
4vO
3the mass ratio being 1:10 ~ 1:20 according to E:F in solution F adds biological carbon E, again the mixture obtained is proceeded in reactor, after reactor is sealed, be placed in hydro-thermal induction heating instrument, with the induction frequencies of 400 ~ 800KHz by room temperature to 160 ~ 220 DEG C, and be incubated 10 ~ 30min, be then cooled to 60 ~ 80 DEG C, insulation 10 ~ 20min, obtains suspension;
(8) suspension centrifugation is obtained powder product, then powder product is used respectively deionized water and soaked in absolute ethyl alcohol and washing, then dry, grinding, obtains NH
4v
3o
8/ C nano compound.
2. the preparation method of a kind of biological carbon/ammonium vanadate anode material for lithium-ion batteries according to claim 1, it is characterized in that, in step (1), biomass precast body is the one in banana skin, shrimp shell, Chinese parasol leaf, wheat stalk or maize straw.
3. the preparation method of a kind of biological carbon/ammonium vanadate anode material for lithium-ion batteries according to claim 1, is characterized in that, in step (1), the size dimension of homogeneous bulky A is 4 ~ 6mm.
4. the preparation method of a kind of biological carbon/ammonium vanadate anode material for lithium-ion batteries according to claim 1, is characterized in that, in step (2) by homogeneous bulky A at room temperature dry 0.5 ~ 1h obtain block B.
5. the preparation method of a kind of biological carbon/ammonium vanadate anode material for lithium-ion batteries according to claim 1, is characterized in that, in step (3), the concentration of red fuming nitric acid (RFNA) is 2 ~ 5molL
-1.
6. the preparation method of a kind of biological carbon/ammonium vanadate anode material for lithium-ion batteries according to claim 1, it is characterized in that, in step (3), the condition of homogeneous reaction is: be incubated 20 ~ 50min after being warming up to 150 DEG C ~ 180 DEG C with the heating rate of 15 DEG C/min, then naturally cool to room temperature.
7. the preparation method of a kind of biological carbon/ammonium vanadate anode material for lithium-ion batteries according to claim 1, it is characterized in that, carbonization in tube-type atmosphere furnace is moved into after being dried by product C suction filtration in step (4), described tube-type atmosphere furnace passes into nitrogen, the condition of carbonization is: tube-type atmosphere furnace is warmed up to 50 DEG C by 10min, after 75min is warmed up to 600 ~ 800 DEG C, and be incubated 60 ~ 180min at this temperature.
8. the preparation method of a kind of biological carbon/ammonium vanadate anode material for lithium-ion batteries according to claim 1, it is characterized in that, in step (8) by powder product by the detailed process of deionized water and soaked in absolute ethyl alcohol and washing be respectively: powder product is first soaked 10 ~ 20min with deionized water, then deionized water is spent 5 ~ 10 times, use soaked in absolute ethyl alcohol 10 ~ 20min again, then use absolute ethanol washing 5 ~ 10 times.
9. the preparation method of a kind of biological carbon/ammonium vanadate anode material for lithium-ion batteries according to claim 1, is characterized in that, the baking temperature in step (8) is 80 ~ 110 DEG C, and the time is 6 ~ 8h.
10. a preparation method for biological carbon/ammonium vanadate anode material for lithium-ion batteries, is characterized in that, comprise the following steps:
(1) Chinese parasol leaf is cleaned remove surface impurity, shred size dimension is the homogeneous bulky A of 4mm;
(2) by homogeneous bulky A at room temperature dry 0.5h obtain block B;
(3) in block B, adding concentration is 2molL
-1red fuming nitric acid (RFNA) after, be incubated 20min after being warming up to 150 DEG C with the heating rate of 15 DEG C/min, then naturally cool to room temperature, obtain product C;
(4) move in tube-type atmosphere furnace after being dried by product C suction filtration and carry out carbonization, tube-type atmosphere furnace passes into nitrogen, and the condition of carbonization is: tube-type atmosphere furnace is warmed up to 50 DEG C by 10min, and 75min is incubated 180min after being warmed up to 600 DEG C, obtains carbonized product D;
(5) carbonized product D is added alcohol immersion, then with distilled water wash wash three times with ethanol again three times after suction filtration, then dry, obtain the charcoal E of loose structure;
(6) be dissolved in deionized water by ammonium metavanadate, obtained concentration is the NH of 0.20mol/L
4vO
3solution F;
(7) by NH
4vO
3the pH value of solution F is adjusted to 0.5, to NH
4vO
3the mass ratio being 1:10 according to E:F in solution F adds biological carbon E, again the mixture obtained is proceeded in reactor, after reactor is sealed, be placed in hydro-thermal induction heating instrument, with the induction frequencies of 400KHz by room temperature to 160 DEG C, and be incubated 10min, be then cooled to 60 DEG C, insulation 10min, obtains suspension;
(8) suspension centrifugation is obtained powder product, powder product is first soaked 10min with deionized water, then deionized water is spent 5 times, use soaked in absolute ethyl alcohol 10min again, then absolute ethanol washing is used 5 times, then dry 6h at the temperature of 80 DEG C, more dried solid product is ground, obtain the NH of porous flake
4v
3o
8/ C nano compound, is biological carbon/ammonium vanadate anode material for lithium-ion batteries.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510141214.5A CN104701498B (en) | 2015-03-27 | 2015-03-27 | A kind of preparation method of biological carbon/ammonium vanadate anode material for lithium-ion batteries |
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|---|---|---|---|
| CN201510141214.5A CN104701498B (en) | 2015-03-27 | 2015-03-27 | A kind of preparation method of biological carbon/ammonium vanadate anode material for lithium-ion batteries |
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| Publication Number | Publication Date |
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| CN105655590A (en) * | 2016-01-15 | 2016-06-08 | 陕西科技大学 | Method for preparing spherical lithium/sodium battery negative electrode carbon material |
| CN106058254A (en) * | 2016-07-07 | 2016-10-26 | 陕西科技大学 | Method for preparing biochar/carbon nano-tubes for cathode materials for sodium ion batteries |
| CN106099096A (en) * | 2016-07-07 | 2016-11-09 | 上海交通大学 | Trimanganese tetroxide nano particulate composite that porous carbon supports and preparation method thereof |
| CN106099089A (en) * | 2016-07-07 | 2016-11-09 | 陕西科技大学 | A kind of preparation method of anode material of lithium-ion battery biological carbon |
| CN106129349A (en) * | 2016-06-27 | 2016-11-16 | 陕西科技大学 | A kind of anode material for lithium-ion batteries ammonium vanadate/Graphene and preparation method thereof |
| CN106207179A (en) * | 2016-07-07 | 2016-12-07 | 陕西科技大学 | The method that a kind of KOH activation pomelo peel prepares sodium-ion battery negative material |
| CN108023086A (en) * | 2017-12-01 | 2018-05-11 | 哈尔滨师范大学 | The method that carbon dioxide catalysis prepares iron-based polyanion-high porosity biomass carbon composite material with multidimensional hierarchy |
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| CN109761276A (en) * | 2018-12-20 | 2019-05-17 | 广东工业大学 | A kind of stratiform ammonium vanadate electrode material and its preparation method and application |
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