AU2021100943A4 - A method of preparing carbon supported transition metal sulfide electrode materials from bio-oil - Google Patents
A method of preparing carbon supported transition metal sulfide electrode materials from bio-oil Download PDFInfo
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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Abstract
The invention is in the technical fields of biomass resources utilization and preparation
of electrode materials, and involves a method of preparing carbon supported transition metal
sulfide electrode materials, especially a preparing method using bio-oil derived from biomass
as carbon source. Typically, the sulfate solution is firstly prepared via dissolving the transition
metal sulfate (such as nickel sulfate or cobalt sulfate) into methanol/water solution. Secondly,
the bio-oil is collected from pyrolyzing biomass at 600-1000°C for 10 to 120 min in a
flowing inert atmosphere. Finally, the carbon supported transition metal sulfide electrode
materials can be obtained after calcined the collected bio-oil containing sulfate and ground.
The prepared electrode materials based on the pyrolysis bio-oil display the superb
supercapacitor performances: more than 1000 F/g at the current density of 1.0 A/g.
Furthermore, the biomass as raw material has the advantages of low price, green
sustainability, and the preparation process is facile and easy for industrial production. Besides,
the invention develops and provides a new way for the high value conversion of biomass
resources and the preparation of carbon-based transition metal sulfide electrode materials.
Pyrolysi Bio-oil
In-situ injection
Methanol/water
solution
S ci t ySulfate solution
Transitiondisle
metal sulfate
Drying
Carbon supported transition metal Grinding Calcination in a hydrogen
sullfide electrode materials rich atmosphere
Figure 1 Flow chart of preparing the carbon supported transition metal sulfide electrode
materials in the invention.
•?Ni3S2
10 20 30 40 50 60 70 80
20 (degree)
Figure 2 XRD pattern of carbon supported Ni3S2 electrode material for embodiment 3 in the
invention.
1/2
Description
Pyrolysi Bio-oil
In-situ injection Methanol/water solution
S ci t ySulfate solution
Transitiondisle metal sulfate
Drying
Carbon supported transition metal Grinding Calcination in a hydrogen sullfide electrode materials rich atmosphere
Figure 1 Flow chart of preparing the carbon supported transition metal sulfide electrode
materials in the invention.
•?Ni3S2
10 20 30 40 50 60 70 80 20 (degree)
Figure 2 XRD pattern of carbon supported Ni3S2 electrode material for embodiment 3 in the
invention.
1/2
A Method of Preparing Carbon Supported Transition Metal Sulfide Electrode Materials
from Bio-oil
Technical Field
This invention involves a method of preparing carbon supported transition metal sulfide
electrode materials, especially a preparing method of carbon supported transition metal
sulfide electrode materials from bio-oil, and is in the technical fields of biomass resources
utilization and preparation of electrode materials.
Background Technology
Electrochemical supercapacitors, as a new type of energy storage device, realize the
mutual conversion between chemical energy and electric energy store energy based on the
electric double layer capacitor and pseudocapacitor mechanisms. The electrochemical
supercapacitors have been widely used in daily life, aerospace, national defense, and other
fields due to the advantages of the long cycle life, fast charge and discharge and high-power
density.
The transition metal sulfides have a 3d electron structure, along with the excellent
optical, electrical, magnetic as well as catalytic performances, and have become a kind of hot
research materials among the inorganic materials. Notably, the nickel sulfides and cobalt
sulfides are considered as the promising electrode materials because of non-toxicity and low
price. However, the individual transition metal sulfides usually exit as the form of
nanoparticles or nanosheets, which is prone to agglomeration or structural collapse during the
long-term charge-discharge cycles, leading to the negative effect on the ultimate
electrochemical performances. In addition, the poor conductivity of transition metal sulfides
also has a negative impact on their electrochemical performances. The invention with the
patent disclosure number of CN108832097A reported a prepared method for preparing the
NiS 2 nanosheets@carbon composites via the hydrothermal reaction, in-situ polymerization of dopamine hydrochloride, and calcination with sulfur powders in sequence. Obviously, the
preparation process is complex and the cost is high for CN108832097A. Biomass acts as the
only renewable carbon source, has the advantages of wide distribution, rich reserves, and low
price. More importantly, 50% ~ 65 wt.% of bio-oil will be produced after the pyrolysis of
biomass. How to realize the high value conversion of bio-oil to carbon supported transition metal sulfide electrode materials has been a hot issue.
Content of the Invention One purpose of the invention is to develop a facile method of preparing carbon supported transition metal sulfide electrode materials based on the pyrolysis bio-oil, and the method should be easily industrialized. Another purpose of the invention is to provide a carbon supported transition metal sulfide electrode materials with excellent supercapacitor performances, and realize high value utilization and conversion of biomass resources. Another purpose of the invention is to provide the electrochemical energy storage application of carbon supported transition metal sulfide electrode materials, and the method should have high commercial value and widely application prospect. The following technical scheme is adopted in the invention, to realize the aforesaid objectives: A method of preparing transition metal sulfide electrode materials from bio-oil concretely involves the following steps: (1) Add the appropriate transition metal sulfate into the prepared absorbent solution of bio-oil to get the sulfate solution, and then which is added into bio-oil collection device; (2) Pyrolyze biomass at 600-1000°C for 10 to 120 min under a flowing nitrogen or argon atmosphere in a tubular furnace connected with the bio-oil collection device mentioned in Step (1) to collect the bio-oil; (3) Dry up and calcinate the collected bio-oil obtained from Step (2) at 450~55 0 °C for 1~3 h under a flowing reducing atmosphere in a tubular furnace to obtain the carbon supported transition metal sulfide electrode materials after cooling down to the ambient temperature. Preferably, the mass ratio of the sulfate solution added into the bio-oil collection device in Step (1) to the biomass added in the tubular furnace in Step (2) is 1: 1, and the bio-oil absorbent solution mentioned in Step (1) is constituted of methanol and water with a volume ratio of 1: 2. Preferably, the transition metal sulfate mentioned in Step (1) is nickel sulfate or cobalt sulfate.
Preferably, the mass concentration of sulfate solution in Step (1) is in a range from 1.0% to
7.0%.
Preferably, the biomass mentioned in Step (2) is not restricted to platanus leaf, and other
biomasses are also applicable such as wood, agricultural waste, animal waste or beyond.
Preferably, the calcination temperature mentioned in Step (3) is in a range from 450°C to
550°C, and the calcination time is in a range from 1 to 3 h.
Preferably, the reducing atmosphere mentioned in Step (3) is a flowing mixed atmosphere
with hydrogen and inert gas, and the volumetric fraction of hydrogen is larger than 10%.
The carbon supported transition metal sulfide electrode materials can be prepared according
to the aforesaid preparation method.
The aforesaid carbon supported transition metal sulfide electrode materials can be applied in
the energy storage field, and exhibit desirable specific capacitances.
The carbon supported transition metal sulfide electrode materials integrate the following
intrinsic advantages: the high conductivity of carbon support and the high pseudocapacitance
of transition metal sulfide. In addition, the existence of carbon support can effectively
improve the dispersion degree of transition metal sulfide. Benefiting from the above
advantages, the carbon supported transition metal sulfide electrode materials present the
exceptional supercapacitor capacitances. In this invention, the low-price and wide source
biomass is used as the raw material, and the carbon supported transition metal sulfide
electrode materials are synthesized based on the pyrolysis bio-oil. When these electrode
materials are applied in supercapacitors, they display the superb supercapacitor performances:
more than 1000 F/g at the current density of 1.0 A/g. The method in this invention is
universal method, and the preparation process is facile and easy for industrial production, and
has good commercial value and application prospect. In addition, the invention develops a
new way for the resource utilization of biomass and the preparation of carbon supported
transition metal sulfide electrode materials.
Beneficial Effects of the Invention:
(1) The invention provides a facile method for preparing carbon supported transition metal
sulfide electrode materials based on the pyrolysis bio-oil from the low-price and wide source biomass, and the method is easy to be industrialized; (2) The transition metal sulfide can be formed via directly direct calcining sulfate in a reducing atmosphere containing hydrogen, which greatly simplifies the preparation process of transition metal sulfide; (3) The carbon supported transition metal sulfide electrode materials is prepared from the pyrolysis bio-oil, which can realize the utilization of biomass resources; (4) The carbon supported transition metal sulfide electrode materials exhibit the excellent supercapacitor performances, high commercial value, and broad prospect, and high value conversion of biomass resources can be realized using the method in this invention.
Description of Attached Figures Figure 1 is the flow chart of preparing the carbon supported transition metal sulfide electrode materials in the invention; Figure 2 is the XRD pattern of carbon supported Ni 3 S 2 electrode material for embodiment 3 in the invention; Figure 3 is the galvanostatic charge-discharge curves of carbon supported Ni 3 S 2 electrode material for embodiment 3 in the invention.
Detailed Description of the Invention The invention will be further described in details in combination with the following embodiments, contrast cases, table and attached figures.
Embodiment 1 In the embodiment, 1.0 wt.% nickel sulfate solution is used to prepare the precursor of electrode material, and then the Ni 3 S 2/C electrode material is received via calcining the precursor at 550°C for 1 h in a flowing reducing atmosphere, followed by evaluating its supercapacitor performances. The detailed synthesizing steps are as follows: (1) Prepare the absorbent solution of bio-oil using the methanol and water with a volume ratio of 1:2, and then fully dissolve nickel sulfate into above solution to get 1.0 wt.% nickel sulfate solution after the magnetic stirring for 40 min, and subsequently take the appropriate nickel sulfate solution (mo) into the bio-oil collection device; (2) Add the equivalent platanus leaves (mo) in the tubular furnace connected with the bio-oil collection device, and then increase the temperature to 600°C and keep for 1 h in a flowing nitrogen atmosphere; (3) Dry up the collected bio-oil at 80°C for over 18 h in an oven, and then add the obtained precursor to a square crucible, calcine at 550°C for 1 h in a flowing atmosphere (H2 : N 2 = 30 mL: 30 mL), and cool down to the ambient temperature in sequence, and finally the Ni 3 S 2 /C electrode material is obtained after ground into powders.
Embodiment 2 In the embodiment, 3.0 wt.% nickel sulfate solution is used to prepare the precursor of electrode material, and then the Ni 3 S 2/C electrode material is received via calcining the precursor at 550°C for 1 h in a flowing reducing atmosphere, followed by evaluating its supercapacitor performances. The detailed synthesizing steps are as follows: (1) Prepare the absorbent solution of bio-oil using the methanol and water with a volume ratio of 1:2, and then fully dissolve nickel sulfate into above solution to get 3.0 wt.% nickel sulfate solution after the magnetic stirring for 40 min, and subsequently take the appropriate nickel sulfate solution (mo) into the bio-oil collection device; (2) Add the equivalent platanus leaves (mo) in the tubular furnace connected with the bio-oil collection device, and then increase the temperature to 600°C and keep for 1 h in a flowing nitrogen atmosphere; (3) Dry up the collected bio-oil at 80°C for over 18 h in an oven, and then add the obtained precursor to a square crucible, calcine at 550°C for 1 h in a flowing atmosphere (H2 : N 2 = 30 mL: 30 mL), and cool down to the ambient temperature in sequence, and finally the Ni 3 S 2 /C electrode material is obtained after ground into powders.
Embodiment 3 In the embodiment, 5.0 wt.% nickel sulfate solution is used to prepare the precursor of electrode material, and then the Ni 3 S 2/C electrode material is received via calcining the precursor at 550°C for 1 h in a flowing reducing atmosphere, followed by evaluating its supercapacitor performances. The detailed synthesizing steps are as follows:
(1) Prepare the absorbent solution of bio-oil using the methanol and water with a volume
ratio of 1:2, and then fully dissolve nickel sulfate into above solution to get 5.0 wt.% nickel
sulfate solution after the magnetic stirring for 40 min, and subsequently take the appropriate
nickel sulfate solution (mo) into the bio-oil collection device;
(2) Add the equivalent platanus leaves (mo) in the tubular furnace connected with the bio-oil
collection device, and then increase the temperature to 600°C and keep for 1 h in a flowing
nitrogen atmosphere;
(3) Dry up the collected bio-oil at 80°C for over 18 h in an oven, and then add the obtained
precursor to a square crucible, calcine at 550°C for 1 h in a flowing atmosphere (H2 : N 2 = 30
mL: 30 mL), and cool down to the ambient temperature in sequence, and finally the Ni 3 S 2 /C
electrode material is obtained after ground into powders.
Embodiment 4
In the embodiment, 7.0 wt.% nickel sulfate solution is used to prepare the precursor of
electrode material, and then the Ni 3 S 2/C electrode material is received via calcining the
precursor at 550°C for 1 h in a flowing reducing atmosphere, followed by evaluating its
supercapacitor performances. The detailed synthesizing steps are as follows:
(1) Prepare the absorbent solution of bio-oil using the methanol and water with a volume
ratio of 1:2, and then fully dissolve nickel sulfate into above solution to get 7.0 wt.% nickel
sulfate solution after the magnetic stirring for 40 min, and subsequently take the appropriate
nickel sulfate solution (mo) into the bio-oil collection device;
(2) Add the equivalent platanus leaves (mo) in the tubular furnace connected with the bio-oil
collection device, and then increase the temperature to 600°C and keep for 1 h in a flowing
nitrogen atmosphere;
(3) Dry up the collected bio-oil at 80°C for over 18 h in an oven, and then add the obtained
precursor to a square crucible, calcine at 550°C for 1 h in a flowing atmosphere (H2 : N 2 = 30
mL: 30 mL), and cool down to the ambient temperature in sequence, and finally the Ni 3 S 2 /C
electrode material is obtained after ground into powders.
Embodiment 5
In the embodiment, 5.0 wt.% nickel sulfate solution is used to prepare the precursor of
electrode material, and then the Ni 3 S 2/C electrode material is received via calcining the
precursor at 450°C for 1 h in a flowing reducing atmosphere, followed by evaluating its
supercapacitor performances. The detailed synthesizing steps are as follows:
(1) Prepare the absorbent solution of bio-oil using the methanol and water with a volume
ratio of 1:2, and then fully dissolve nickel sulfate into above solution to get 5.0 wt.% nickel
sulfate solution after the magnetic stirring for 40 min, and subsequently take the appropriate
nickel sulfate solution (mo) into the bio-oil collection device;
(2) Add the equivalent platanus leaves (mo) in the tubular furnace connected with the bio-oil
collection device, and then increase the temperature to 600°C and keep for 1 h in a flowing
nitrogen atmosphere;
(3) Dry up the collected bio-oil at 80°C for over 18 h in an oven, and then add the obtained
precursor to a square crucible, calcine at 450°C for 1 h in a flowing atmosphere (H2 : N 2 = 30
mL: 30 mL), and cool down to the ambient temperature in sequence, and finally the Ni 3 S 2 /C
electrode material is obtained after ground into powders.
Embodiment 6
In the embodiment, 5.0 wt.% cobalt sulfate solution is used to prepare the precursor of
electrode material, and then the Co9 S 8/C electrode material is received via calcining the
precursor at 550°C for 1 h in a flowing reducing atmosphere, followed by evaluating its
supercapacitor performances. The detailed synthesizing steps are as follows:
(1) Prepare the absorbent solution of bio-oil using the methanol and water with a volume
ratio of 1:2, and then fully dissolve cobalt sulfate into above solution to get 5.0 wt.% cobalt
sulfate solution after the magnetic stirring for 40 min, and subsequently take the appropriate
cobalt sulfate solution (mo) into the bio-oil collection device;
(2) Add the equivalent platanus leaves (mo) in the tubular furnace connected with the bio-oil
collection device, and then increase the temperature to 600°C and keep for 1 h in a flowing
nitrogen atmosphere;
(3) Dry up the collected bio-oil at 80°C for over 18 h in an oven, and then add the obtained precursor to a square crucible, calcine at 550°C for 1 h in a flowing atmosphere (H2 : N 2 = 30 mL: 30 mL), and cool down to the ambient temperature in sequence, and finally the Co9 S8 /C electrode material is obtained after ground into powders.
Embodiment 7
In the embodiment, 5.0 wt.% cobalt sulfate solution is used to prepare the precursor of
electrode material, and then the Co9 S 8/C electrode material is received via calcining the
precursor at 550°C for 3 h in a flowing reducing atmosphere, followed by evaluating its
supercapacitor performances. The detailed synthesizing steps are as follows:
(1) Prepare the absorbent solution of bio-oil using the methanol and water with a volume
ratio of 1:2, and then fully dissolve cobalt sulfate into above solution to get 5.0 wt.% cobalt
sulfate solution after the magnetic stirring for 40 min, and subsequently take the appropriate
cobalt sulfate solution (mo) into the bio-oil collection device;
(2) Add the equivalent platanus leaves (mo) in the tubular furnace connected with the bio-oil
collection device, and then increase the temperature to 600°C and keep for 1 h in a flowing
nitrogen atmosphere;
(3) Dry up the collected bio-oil at 80°C for over 18 h in an oven, and then add the obtained
precursor to a square crucible, calcine at 550°C for 3 h in a flowing atmosphere (H2 : N 2 = 30
mL: 30 mL), and cool down to the ambient temperature in sequence, and finally the Co9 S8 /C
electrode material is obtained after ground into powders.
Contrast case 1
In the contrast case, the nanoporous carbon is synthesized by directly calcining the
pyrolytic bio-oil in a flowing reducing atmosphere, and subsequently the supercapacitor
performances are evaluated. The detailed synthesizing steps are as follows:
(1) Prepare the absorbent solution of bio-oil using the methanol and water with a volume
ratio of 1:2 via stirring for 40 min, and subsequently take the appropriate solution (mo) into
the bio-oil collection device;
(2) Add the equivalent platanus leaves (mo) in the tubular furnace connected with the bio-oil
collection device, and then increase the temperature to 600°C and keep for 1 h in a flowing nitrogen atmosphere;
(3) Dry up the collected bio-oil at 80°C for over 18 h in an oven, and then add the obtained
precursor to a square crucible, calcine at 550°C for 1 h in a flowing atmosphere (H2 : N 2 = 30
mL: 30 mL), and cool down to the ambient temperature in sequence, and finally the
nanoporous carbon electrode material is obtained after ground into powders.
Contrast case 2
In the contrast case, 5.0 wt.% nickel sulfate solution is used to synthesize the Ni3 S 2
electrode material, which is received via calcining the obtained nickel sulfate at 550°C for 1 h
in a flowing reducing atmosphere, followed by evaluating its supercapacitor performances.
The detailed synthesizing steps are as follows:
(1) Prepare the absorbent solution of bio-oil using the methanol and water with a volume
ratio of 1:2, and then fully dissolve nickel sulfate into above solution to get 5.0 wt.% nickel
sulfate solution after the magnetic stirring for 40 min;
(2) Dry up the nickel sulfate solution at 80°C for over 18 h in an oven, and then add the
obtained nickel sulfate to a square crucible, calcine at 550°C for 1 h in a flowing atmosphere
(H 2 : N 2 = 30 mL: 30 mL), and cool down to the ambient temperature in sequence, and finally
the Ni 3 S 2 electrode material is obtained after ground into powders.
Contrast case 3
In the contrast case, 5.0 wt.% cobalt sulfate solution is used to synthesize the Co9 S8
electrode material, which is received via calcining the obtained cobalt sulfate at 550°C for 1 h
in a flowing reducing atmosphere, followed by evaluating its supercapacitor performances.
The detailed synthesizing steps are as follows:
(1) Prepare the absorbent solution of bio-oil using the methanol and water with a volume
ratio of 1:2, and then fully dissolve cobalt sulfate into above solution to get 5.0 wt.% cobalt
sulfate solution after the magnetic stirring for 40 min;
(2) Dry up the cobalt sulfate solution at 80°C for over 18 h in an oven, and then add the
obtained cobalt sulfate to a square crucible, calcine at 550°C for 1 h in a flowing atmosphere
(H 2 : N 2 = 30 mL: 30 mL), and cool down to the ambient temperature in sequence, and finally the Co9 S 8 electrode material is obtained after ground into powders.
Evaluation on the supercapacitor performances of electrode materials. Typically,
the 8.0 mg of sample, 1.0 mg of acetylene black, 1 mg PVDF are well mixed, and then 100
L of absolute alcohol is added to the above mixture to prepare slurry. Subsequently, the
slurry is coated onto 1 x 2 cm2 pretreated foam nickel and dried at 80°C for over 18 h.
Afterwards, the electrode with thickness of 0.2 mm can be obtained via pressing the foam
nickel on a tablet press under the pressure of 2.0 MPa and maintaining for 10 s. Finally, the
characterizations of supercapacitor performance were performed on an electrochemical
workstation (Chenhua CH660E) in 6 mol/L KOH aqueous solution with a standard
three-electrode system: the prepared electrode (working electrode), a platinum plate (counter
electrode) and a Hg/HgO electrode (reference electrode). The results are summarized in
Table 1.
Table 1 The process parameters of preparing electrode materials and the supercapacitor
performances of electrode materials in the contrast cases and all embodiments of the
invention.
Sulfate Calcination Calcination Specific
No. Sulfate Concentration Temperature Time Capacitance
(wt.%) ( 0 C) (h) (F/g)
Contrast Case1 - - 550 1 152
Contrast Case 2 Nickel sulfate 5.0 550 1 347
Contrast Case 3 Cobalt sulfate 5.0 550 1 215
Embodiment 1 Nickel sulfate 1.0 550 1 684
Embodiment 2 Nickel sulfate 3.0 550 1 821
Embodiment 3 Nickel sulfate 5.0 550 1 1002
Embodiment 4 Nickel sulfate 7.0 550 1 853
Embodiment 5 Nickel sulfate 5.0 450 1 846
Embodiment 6 Cobalt sulfate 5.0 550 1 964
Embodiment 7 Cobalt sulfate 5.0 550 3 928
Table 1 lists out the process parameters of preparing electrode materials and the
supercapacitor performances of electrode materials in the contrast cases and all embodiments
of the invention. It can be found from Table 1 that the carbon supported transition metal
sulfide electrode materials have the optimum supercapacitor performances by adopting the
metal sulfate solution of 5.0 wt.%, the calcination temperature of 600°C and the calcination
time of 1 h. It can be found by comparing all contrast cases that the metal sulfides have the
higher specific capacitances than the nanoporous carbon. Comparing the embodiments 1~4
with the contrast cases 1 and 2 (or comparing the embodiments 6 and 7 with the contrast
cases 1 and 3), it can be found that the specific capacitances of carbon supported transition
metal sulfide electrode materials (Embodiments 1-7) are larger than the sum of specific
capacitances for the nanoporous carbon (Contrast cases 1) and metal sulfide (Contrast cases 2
or 3), suggesting that the nanoporous carbon can effectively disperse and stabilize metal
sulfides in the carbon supported transition metal sulfide electrode materials, and significantly
improve the supercapacitor performances of electrode materials. As shown in the
embodiments 1~4, there is an optimal mass ratio of metal sulfide to nanoporous carbon.
Specifically, when the value is larger than the optimal mass ratio, there is less nanoporous
carbon, leading to the decreased conductivities and lower specific capacitances of in the
carbon supported transition metal sulfide electrode materials. When the value is less than the
optimal mass ratio, there is less metal sulfide, resulting in the decreased contribution ratio of
pseudocapacitance and lower specific capacitances of the carbon supported transition metal
sulfide electrode materials. Figure 2 shows the XRD pattern of carbon supported transition
Ni 3 S 2 electrode material (Embodiment 3), which proves that the nickel atoms exist as the form of Ni 3S2 phase. Figure 3 displays the galvanostatic charge-discharge curves of carbon
supported Ni 3S 2 electrode material (Embodiment 3). It can be determined from Figure 3 that
the high capacitance of carbon supported Ni 3S 2 electrode material is attributed to the pseudocapacitance of Ni3 S 2 phase.
Besides, in the case that other reaction parameters are same as those in embodiment 3,
the following results can be received. When methanol is substituted for alcohol, the specific
capacitances of electrode materials remain unchanged. With the further increase in the
concentration of sulfate solution, the specific capacitances of electrode materials drop sharply.
When wood, agricultural waste, water hyacinth or animal manure is used instead of platanus
leaves, the electrode materials still render the high specific capacitances, indicating that the
preparing method in the invention has universality for biomass. When the biomass is
pyrolyzed was at 600°C ~ 1000°C for different holding time (10-120 min), electrode
materials also have the high specific capacitances (more than 650 F/g). When the lower
calcination temperature (300~400°C) is adopted, the metal sulfide cannot be formed. When
the higher calcination temperature (600~ 800°C) is used, the metal sulfide is obviously
sintered, leading to the tiny specific capacitances of electrode materials. When the volumetric
concentration of hydrogen is lower than 5% in the reducing atmosphere, the metal sulfate
cannot be completely changed into sulfide after calcining for 3 h. When the hydrogen
concentration is higher than 10%, the metal sulfate can be completely converted into sulfide
after calcining for 3 h. When the hydrogen concentration is higher than 20%, the metal sulfate
can be completely transformed into sulfide after calcining for 1 h.
Certainly, the above description isn't merely restricted to the above embodiments, and
the technical characteristics unmentioned in the invention can be realized by adopting current
technologies, which are not reiterated here. The above embodiments and attached figures are
merely used to describe the technical scheme of the invention but not restrict the invention.
The invention is described in details by referring to the preferred embodiments. The general
technicians in related fields should understand that the changes, modifications, additions, or
replacement made within the essential scope of the invention are also in accordance with the
tenet of the invention, and should be included in the protective scope specified in the claims
of the invention.
Claims (9)
1. A method of preparing carbon supported transition metal sulfide electrode materials is
characterized by adopting the following steps:
(1) Add the appropriate transition metal sulfate into the prepared absorbent solution of bio-oil
to get the sulfate solution, and then which is added into bio-oil collection device;
(2) Pyrolyze biomass at 600~1000°C for 10 to 120 min under a flowing nitrogen or argon
atmosphere in a tubular furnace connected with the bio-oil collection device mentioned in
Step (1) to collect the bio-oil;
(3) Dry up and calcinate the collected bio-oil obtained from Step (2) at 450~550°C for 1~3 h
under a flowing reducing atmosphere in a tubular furnace to obtain the carbon supported
transition metal sulfide electrode materials after cooling down to the ambient temperature.
2. The method described in Claim 1 is characterized as follows: the mass ratio of the sulfate
solution added into the bio-oil collection device in Step (1) to the biomass added in the
tubular furnace in Step (2) is 1: 1, and the bio-oil absorbent solution mentioned in Step (1) is
constituted of methanol and water with a volume ratio of 1: 2.
3. The method described in Claim 1 is characterized as follows: the transition metal sulfate
mentioned in Step (1) is nickel sulfate or cobalt sulfate.
4. The method described in Claim 1 is characterized as follows: the mass concentration of
sulfate solution in Step (1) is in a range from 1.0 % to 7.0 %.
5. The method described in Claim 1 is characterized as follows: the biomass mentioned in
Step (2) is platanus leaf, wood, agricultural waste, animal manure or beyond.
6. The method described in Claim 1 is characterized as follows: the calcination temperature
mentioned in Step (3) is in a range from 450°C to 550°C, and the calcination time is in a
range from 1 to 3 h.
7. The method described in Claim 1 is characterized as follows: the reducing atmosphere
mentioned in Step (3) is a flowing mixed atmosphere with hydrogen and inert gas, and the
volumetric fraction of hydrogen is larger than 10%.
8. According to any items of Claim 1-7, the carbon supported transition metal sulfide
electrode materials can be prepared.
9. The electrode materials mentioned in Claim 8 are characterized as follows: the electrode materials deliver the superb supercapacitor performances for the electrochemical energy storage.
Figure 1 Flow chart of preparing the carbon supported transition metal sulfide electrode materials in the invention.
Figure 2 XRD pattern of carbon supported Ni3S2 electrode material for embodiment 3 in the invention.
1/2
Figure 3 Galvanostatic charge-discharge curves of carbon supported Ni3S2 electrode material for embodiment 3 in the invention.
2/2
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| CN202011570195.5A CN112551508B (en) | 2020-12-26 | 2020-12-26 | Method for preparing carbon-based transition metal sulfide composite electrode material based on pyrolytic bio-oil |
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| CN114790397A (en) * | 2022-06-23 | 2022-07-26 | 中国农业科学院农业环境与可持续发展研究所 | Method for preparing electrode material by polymerizing and modifying biomass pyrolysis oil |
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| CN110112007B (en) * | 2019-05-20 | 2021-03-02 | 哈尔滨工业大学 | Preparation method of pea pod-shaped carbon-coated transition metal sulfide composite electrode material |
| CN110980858B (en) * | 2019-11-25 | 2021-10-01 | 中国科学技术大学 | Method for removing halogenated organic matters in sewage |
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| CN114790397A (en) * | 2022-06-23 | 2022-07-26 | 中国农业科学院农业环境与可持续发展研究所 | Method for preparing electrode material by polymerizing and modifying biomass pyrolysis oil |
| CN114790397B (en) * | 2022-06-23 | 2023-02-03 | 中国农业科学院农业环境与可持续发展研究所 | Method for preparing electrode material by polymerizing and modifying biomass pyrolysis oil |
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