CN106920966A - A kind of carbon-based lithium ion cell negative electrode material and its preparation using sludge as precursor - Google Patents
A kind of carbon-based lithium ion cell negative electrode material and its preparation using sludge as precursor Download PDFInfo
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- CN106920966A CN106920966A CN201710235576.XA CN201710235576A CN106920966A CN 106920966 A CN106920966 A CN 106920966A CN 201710235576 A CN201710235576 A CN 201710235576A CN 106920966 A CN106920966 A CN 106920966A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of carbon-based lithium ion cell negative electrode material using sludge as precursor and its preparation, during preparation, first by the pre- carbonization treatment of sludge after, successively through pickling, alkali activate after washing, drying.Compared with prior art, the present invention can realize the recycling of sludge, environmental protection, preparation process is simple, low production cost, and the specific surface area and specific capacity of the carbon-based lithium ion cell negative electrode material for preparing are high, and good cycle has a extensive future.
Description
Technical field
The invention belongs to electrode material manufacturing technology field, it is related to a kind of carbon-based lithium ion battery using sludge as precursor
Negative material and its preparation.
Background technology
Lithium ion battery is dirty with high-energy, high working voltage, high security, environment compared with traditional secondary cell
The advantages of contaminating small.Wherein, negative material stores up the main body of lithium as lithium ion battery, and lithium ion can be realized in charge and discharge process
Insertion and abjection, be the key for improving the performances such as lithium ion battery total specific capacity, cycle performance, discharge and recharge.In negative material
In, all the time all in occupation of main status, in lithium ion battery on sale, the overwhelming majority uses graphitization to carbon based negative electrodes material
Carbon based negative electrodes material.However, the theoretical specific capacity of graphite only has 372mAh/g, which greatly limits the performance of lithium ion battery.
Therefore, exploring the new carbon negative pole material with height ratio capacity becomes study hotspot.
Biomass carbon material, is such as all kinds of plants, animal wastes, timber, city and the industry by the biomass containing carbon rich
Discarded object, woods agricultural wastes etc., by carbonization, the solid product of pyrolysis.It is with low cost because it has wide material sources
The advantages of, it is the desirable feedstock for producing carbon material.Wherein, municipal sludge is one of municipal solid wastes, with Chinese society
Expanding economy, growth in the living standard, the attention rate of environmental problem is also increasingly improved, and green economy and sustainable development turn into
The theme of future development.In recent years, the more attention and the fast development of Development of China's Urbanization with country to water pollution problems,
The scale and sludge yield of municipal sewage plant are continuously increased, it is estimated that this year, about 35,000,000 tons of the sludge yield in the whole nation (contained
Water is 97% or so).Technology with sewage disposal constantly improves, increasingly strict, the sewage disposal effect of sewage drainage standard
Rate is obviously improved, but municipal sludge yield also quickly increases simultaneously so that the disposal pressure of municipal sludge is increasing.
How minimizing, resource, the stabilisation always study hotspot of sludge, at present, domestic main side to Treatment of Sludge are realized
Formula has compost, pyrolysis, burning, digestion etc..However, the research emphasis on pyrolyzing sludge mostly concentrate on reduction Treatment of Sludge
Cost, reduces energy consumption and realizes the aspects such as sludge reduction, and the pyrolyzing sludge biomass carbon for being obtained after pyrolyzing sludge is provided
The research that source utilizes is simultaneously few.It is also a kind of important renewable resource, much due to containing abundant organic matter in sludge
Sludge is all turned waste into wealth in actively research and exploration in country, develops wherein abundant biomass energy, realizes waste resource
Change and utilize.Wherein, there is important environment, social and economic benefit for raw material prepares electrode material using sludge.
But, in existing technique, the species and component requirements to sludge are harsh, greatly limit the selection model of sludge
Enclose, there is larger limitation, poor universality, it is impossible to industrial application.
The content of the invention
The purpose of the present invention be exactly provided for the defect for overcoming above-mentioned prior art to exist a kind of chemical property it is good,
Low cost, the carbon-based lithium ion cell negative electrode material using sludge as precursor of environmental protection and its preparation.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of preparation method of the carbon-based lithium ion cell negative electrode material using sludge as precursor, the method specifically include with
Lower step：
(1) will be placed in tube furnace after sludge pretreatment, and pre- carbonization treatment is carried out under the protection of inert gas, obtained
Pre- carbonized product；
(2) after pre- carbonized product is ground, it is placed in hydrofluoric acid, and stirs 1-24h, washs afterwards and dry；
(3) and then again it is placed in alkaline solution, and stirs 1-24h, dries afterwards and grind；
(4) it is placed in tube furnace, and secondary carbonization treatment is carried out under the protection of inert gas, obtains secondary carbonization and produce
Thing；
(5) by secondary carbonized product be placed in watery hydrochloric acid soak 1-20 days, it is scrubbed, drying after, that is, obtain described in
Sludge as precursor carbon-based lithium ion cell negative electrode material.
Wherein, the purpose of sludge pretreatment is：The water in sludge is sloughed, so that sludge carries out pyrolysis processing.
The purpose of pre- carbonization treatment is：It is biological carbon by the organic matter pyrolysis in sludge.
The purpose of inert gas shielding is：Prevent from being pyrolyzed the carbon material for obtaining to be oxidized.
The purpose that pre- carbonized product is mixed with hydrofluoric acid is：With the silicon in sludge as masterplate, increase the ratio of carbon material
Surface area.
With alkaline solution mix purpose be：Make alkali that activation is fully blended with carbon material, be that secondary carbonization is prepared.
The purpose of secondary carbonization treatment is：Using the high temperature dehydration property of the alkali such as potassium hydroxide, hydrogen, the oxygen in material are reduced
Content.
The purpose of immersion is in watery hydrochloric acid：Remove the impurity in material.
In step (1), described sludge includes primary sludge, excess sludge, dewatered sludge, digested sludge or humus sludge
In one or more.
In step (1), described preprocessing process is：Sludge is ground after cold dry-cure, described cold dry place
The temperature of reason is -50 DEG C to -30 DEG C, and the time is 1-96h.
After sludge is through cold dry-cure, particle diameter is ground to for 50-200 mesh.
In step (1) and step (4), described inert gas is nitrogen or argon gas.
In step (1), the temperature of described pre- carbonization treatment is 400-600 DEG C, and the time is 1-48h；In step (4), institute
The temperature of the secondary carbonization treatment stated is 700-1000 DEG C, and the time is 1-48h.
In step (2), the weight/mass percentage composition of hydrogen fluoride is 0.5-40% in described hydrofluoric acid, and described pre- carbonization is produced
Thing is 1 with the mass ratio of hydrofluoric acid:0.1-10.
In step (3), described alkaline solution is potassium hydroxide aqueous solution, potassium hydroxide in the potassium hydroxide aqueous solution
Weight/mass percentage composition is 5-30%, and described potassium hydroxide and the mass ratio of the pre- carbonized product described in step (2) is 1:1-
10。
In step (5), the weight/mass percentage composition of HCl is 0.5-10% in described watery hydrochloric acid, and described secondary carbonization is produced
Thing is 1 with the mass ratio of watery hydrochloric acid:1-20.
A kind of carbon-based lithium ion cell negative electrode material using sludge as precursor for using described method to be prepared from.
Changing waste into resources problem of the present invention for municipal sludge, it is proposed that one kind is respectively provided with general for all kinds of municipal sludges
The pyrolysis processing scheme of adaptive, meeting on the basis of " resource, minimizing, innoxious ", in solving conventional process scheme
The problems such as process object is limited, and be masterplate using Si contained in sludge, using the loose structure feature of Si to gained
Carbon material carries out structure and reinvents, considerably increase pyrolysis gained carbon material specific surface area so that with its as raw material obtained in
The capacitive property of carbon-based lithium ion cell negative electrode material has obtained significantly improving.
Compared with prior art, the invention has the characteristics that：
1) the precursor sludge used by the present invention is common municipal solid wastes, containing abundant biomass carbon resource,
Wide material sources, it is cheap, realize that its recycling has society very high and environmental benefit, to realizing Green Sustainable
It is significant, because doping has the elements such as K, Al, N, Cu, Fe, Zn in sludge, is conducive to improving carbon-based lithium ion battery
The reversible capacity and cycle performance of negative material, make surface SEI films preferably be modified, so as to be conducive to the diffusion of lithium, together
When, the carbon-based lithium ion cell negative electrode material for preparing has specific surface area very high, and with porous channel structure, can
To improve embedding lithium capacity and charge-discharge performance；
2) preparation process is simple, easily operation, it is adaptable to which all kinds of sludge of domestic sewage factory, practical application is wide, and profit
With the loose structure feature of Si, with it as masterplate, the surface area of the carbon material obtained after treatment has obtained significantly being lifted, and makes
The electrode material that must be prepared using it has specific capacity very high, and cost of material and process costs are relatively low, with important
Social economic environment benefit, can carry out recycling by discarded sludge, realize changing waste into resources, and environmental protection has
Good application prospect；
3) the mesoporous carbon-based lithium ion cell negative electrode material for preparing, the specific discharge capacity after first charge-discharge circulation
970mAh/g is reached as high as, first charge-discharge efficiency is up to 82.5%, after 100 times circulate, coulombic efficiency stabilization exists
More than 98%, capability retention is more than 95%, good cycle.
Brief description of the drawings
Fig. 1 is composed for the SEM (SEM) of the carbon-based lithium ion cell negative electrode material prepared in embodiment 1
Figure；
Fig. 2 is composed for the transmission electron microscope (TEM) of the carbon-based lithium ion cell negative electrode material prepared in embodiment 1
Figure；
Fig. 3 can (XPS) spectrum for the x-ray photoelectron of the carbon-based lithium ion cell negative electrode material prepared in embodiment 1
Figure；
Fig. 4 is the examination of infrared spectrum spectrogram of carbon-based lithium ion cell negative electrode material prepared in embodiment 1；
Fig. 5 is the carbon-based lithium ion cell negative electrode material prepared in embodiment 1 in charge and discharge cycles test process
When m- voltage-to-current figure；
Fig. 6 is the efficiency specific capacity curve map of carbon-based lithium ion cell negative electrode material prepared in embodiment 1.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.The present embodiment is with technical solution of the present invention
Premised on implemented, give detailed implementation method and specific operating process, but protection scope of the present invention is not limited to
Following embodiments.
Embodiment 1：
By grind into powder after the cold dry 96h of primary sludge, it is placed in tube furnace, under nitrogen protection 500 DEG C of carbonization treatments
8h, gained carbon materials abrasive lapping uses distilled water washing and drying after 4h is mixed in 10% hydrofluoric acid solution；Dry gained
Carbon material is with potassium hydroxide with 1:Add appropriate distilled water to mix 8h after 5 ratio mixing, dry and pipe is placed in after grinding
In formula stove under nitrogen protection 800 DEG C be carbonized again；Gained carbon material soaks 10h in 5% watery hydrochloric acid, is dried with distillation water washing
Gained carbon material is used as lithium ion battery negative material after dry.
BET tests are carried out to the carbon-based lithium ion cell negative electrode material, and by the result and using obtained in conventional art
Sludge carbon electrode material is contrasted, as a result as shown in table 1.As can be seen from Table 1, carbon-based lithium ion electricity obtained in the present embodiment
The specific surface area of pond negative material is increased substantially, and the aperture size of material is smaller, with prominent advantage.
Table 1
| Material source | Aperture (nm) | |
| Embodiment 1 | 1866.199 | 3.073 |
| Conventional art | 609.4 | 12.13 |
Fig. 1 is the SEM image of the carbon-based lithium ion cell negative electrode material for preparing.Can be with by Fig. 1
Find out, the carbon-based lithium ion cell negative electrode material has loose porous structure.
Fig. 2 is the transmission electron microscope figure of the carbon-based lithium ion cell negative electrode material for preparing.Can be seen by Fig. 2
Go out, the surface of the carbon-based lithium ion cell negative electrode material shows thickly dotted hole and gap, has confirmed seen in SEM
Material surface it is loose porous the characteristics of.
Fig. 3 is the full spectrogram of x-ray photoelectron power spectrum of the carbon-based lithium ion cell negative electrode material for preparing.Can by Fig. 3
To find out, in addition to carbon, it is rich in the elements such as nitrogen, oxygen, iron.After measured, its phosphorus content be 80.1%, show carbon-based lithium from
The purity of carbon is higher in sub- cell negative electrode material；Nitrogen content is 2.4%, and the doping of nitrogen is favorably improved the electrochemistry of material
Activity and capacitive property, on the other hand to also illustrate that and prepare carbon-based lithium ion cell negative electrode material using this method, do not need to carry out
Domestication, just can make to contain appropriate N element in final obtained carbon-based lithium ion cell negative electrode material.
Fig. 4 is the examination of infrared spectrum figure of the carbon-based lithium ion cell negative electrode material for preparing.Organised according to typical case
The infrared spectrum signature analysis of compound understands there is N-H, C ≡ C, aromatic ring frame (C in the carbon-based lithium ion cell negative electrode material
=C), the structure of functional groups such as C-O.
Fig. 5 is when m- electricity of the carbon-based lithium ion cell negative electrode material for preparing in charge and discharge cycles test process
Piezo-electric flow graph.As seen from Figure 5, with the carbon-based lithium ion cell negative electrode material as raw material obtained in negative material assemble
To lithium battery in charge and discharge cycles test process, electric current, voltage show stabilization periodic cycle wave characteristic.
Fig. 6 is the cycle efficieny specific capacity curve map of the carbon-based lithium ion cell negative electrode material for preparing.Can be with by Fig. 6
Find out, the lithium battery that negative material assembling obtained in the carbon-based lithium ion cell negative electrode material as raw material is obtained is in charge and discharge first
Specific discharge capacity after electricity circulation reaches 970mAh/g, and first charge-discharge efficiency is 73.5%, after 100 times circulate, capacity
Conservation rate is 97.1%.
Embodiment 2：
Grind into powder after the cold dry 48h of dewatered sludge is put into tube furnace, be put into tube furnace under nitrogen protection
Then 550 DEG C of carbonization treatment 6h, the carbon material grind into powder for obtaining is placed in 15% hydrofluoric acid solution and mixes 4h,
Solution is washed with distilled water to again in neutrality, drying；By dried carbon material and potassium hydroxide with 1:4 ratio mixing, and
Add appropriate distilled water to carbon material is flooded, mix 7h, dry and grind；Then carbon material is put into tube furnace,
Nitrogen is protected lower 850 DEG C and is carbonized again；The carbon material for obtaining soaks 10h in being placed on 4% watery hydrochloric acid, is washed with distilled water to solution
In neutrality, the carbon material for obtaining is used as lithium ion battery negative material.
After tested, the carbon material of gained is used as lithium ion battery negative material, the electric discharge ratio after first charge-discharge circulation
Capacity 830mAh/g, first charge-discharge efficiency is 77.6%, and after 100 times circulate, capability retention is 95.8%.
Embodiment 3：
Grind into powder after the cold dry 60h of digested sludge is put into tube furnace, is put under nitrogen protection 500 in tube furnace
Then DEG C carbonization treatment 7h, the carbon material grind into powder for obtaining is placed in 20% hydrofluoric acid solution and mixes 4h, then use
Distillation water washing is to solution in neutrality, drying；By dried carbon material and potassium hydroxide with 1:3 ratio is mixed and added into fitting
Amount distilled water mixes 8h to carbon material is flooded, and dries and grinds；Then carbon material is put into tube furnace, is protected in nitrogen
Lower 800 DEG C are protected to be carbonized again；The carbon material for obtaining soaks 12h in being placed on 6% watery hydrochloric acid, is washed with distilled water to during solution is in
Property, the carbon material for obtaining is used as lithium ion battery negative material.
After tested, the carbon material of gained is used as lithium ion battery negative material, the electric discharge ratio after first charge-discharge circulation
Capacity 620mAh/g, first charge-discharge efficiency is 81.9%, and after 100 times circulate, capability retention is 96.8%.
Embodiment 4：
Grind into powder after the cold dry 72h of excess sludge is put into tube furnace, is put under nitrogen protection 600 in tube furnace
Then DEG C carbonization treatment 8h, the carbon material grind into powder for obtaining is placed in 30% hydrofluoric acid solution and mixes 6h, then use
Distillation water washing is to solution in neutrality, drying；By dried carbon material and potassium hydroxide with 1:4 ratio mixing, and add
Appropriate distilled water mixes 10h to carbon material is flooded, and dries and grinds；Then carbon material is put into tube furnace, in nitrogen
Lower 900 DEG C are protected to be carbonized again；The carbon material for obtaining soaks 12h in being placed on 8% watery hydrochloric acid, is washed with distilled water to during solution is in
Property, the carbon material for obtaining is used as lithium ion battery negative material.
After tested, the carbon material of gained is used as lithium ion battery negative material, the electric discharge ratio after first charge-discharge circulation
Capacity 810mAh/g, first charge-discharge efficiency is 77.3%, and after 100 times circulate, capability retention is 96.3%.
Embodiment 5：
Grind into powder after the cold dry 72h of humus sludge is put into tube furnace, is put under nitrogen protection 700 in tube furnace
Then DEG C carbonization treatment 7h, the carbon material grind into powder for obtaining is placed in 20% hydrofluoric acid solution and mixes 4h, then use
Distillation water washing is to solution in neutrality, drying；By dried carbon material and potassium hydroxide with 1:3 ratio is mixed and added into fitting
Amount distilled water mixes 8h to carbon material is flooded, and dries and grinds；Then carbon material is put into tube furnace, is protected in nitrogen
Lower 1000 DEG C are protected to be carbonized again；The carbon material for obtaining soaks 12h in being placed on 7% watery hydrochloric acid, is washed with distilled water to during solution is in
Property, the carbon material for obtaining is used as lithium ion battery negative material.
After tested, the carbon material of gained is used as lithium ion battery negative material, the electric discharge ratio after first charge-discharge circulation
Capacity 850mAh/g, first charge-discharge efficiency is 82.5%, and after 100 times circulate, capability retention is 95.7%.
Embodiment 6：
A kind of carbon-based lithium ion cell negative electrode material using sludge as precursor, its preparation method specifically includes following step
Suddenly：
(1) primary sludge is ground after cold dry-cure 96h at temperature is for -50 DEG C, then is placed in tube furnace, and in nitrogen
Protection under, temperature be 400 DEG C under conditions of pre- carbonization treatment 48h, obtain pre- carbonized product；
(2) after pre- carbonized product is ground, it is placed in hydrofluoric acid, and stirs 12h, washs afterwards and dry, wherein, hydrogen fluorine
The weight/mass percentage composition of hydrogen fluoride is 20% in acid, and pre- carbonized product is 1 with the mass ratio of hydrofluoric acid:1；
(3) and then again it is placed in potassium hydroxide aqueous solution, and stirs 24h, dries afterwards and grind, wherein, potassium hydroxide
The weight/mass percentage composition of potassium hydroxide is 5% in the aqueous solution, and potassium hydroxide is 1 with the mass ratio of pre- carbonized product in step (2):
10；
(4) it is placed in tube furnace, and under the protection of argon gas, secondary carbonization treatment under conditions of being 850 DEG C in temperature
23h, obtains secondary carbonized product；
(5) secondary carbonized product is placed in watery hydrochloric acid and is soaked 1 day, after scrubbed, drying, that is, obtained using sludge as preceding
The carbon-based lithium ion cell negative electrode material of body, wherein, the weight/mass percentage composition of HCl is 10%, secondary carbonized product in watery hydrochloric acid
It is 1 with the mass ratio of watery hydrochloric acid:1.
Embodiment 7：
A kind of carbon-based lithium ion cell negative electrode material using sludge as precursor, its preparation method specifically includes following step
Suddenly：
(1) excess sludge and dewatered sludge are ground after cold dry-cure 1h at temperature is for -30 DEG C, then is placed in tube furnace
In, and under the protection of argon gas, pre- carbonization treatment 1h under conditions of being 600 DEG C in temperature obtains pre- carbonized product；
(2) after pre- carbonized product is ground, it is placed in hydrofluoric acid, and stirs 24h, washs afterwards and dry, wherein, hydrogen fluorine
The weight/mass percentage composition of hydrogen fluoride is 0.5% in acid, and pre- carbonized product is 1 with the mass ratio of hydrofluoric acid:10；
(3) and then again it is placed in potassium hydroxide aqueous solution, and stirs 1h, dries afterwards and grind, wherein, potassium hydroxide water
The weight/mass percentage composition of potassium hydroxide is 30% in solution, and potassium hydroxide is 1 with the mass ratio of pre- carbonized product in step (2):
1；
(4) it is placed in tube furnace, and under the protection of argon gas, secondary carbonization treatment under conditions of being 700 DEG C in temperature
48h, obtains secondary carbonized product；
(5) by secondary carbonized product be placed in watery hydrochloric acid soak 20 days, it is scrubbed, drying after, that is, obtain using sludge as
The carbon-based lithium ion cell negative electrode material of precursor, wherein, the weight/mass percentage composition of HCl is 0.5% in watery hydrochloric acid, and secondary carbonization is produced
Thing is 1 with the mass ratio of watery hydrochloric acid:20.
Embodiment 8：
A kind of carbon-based lithium ion cell negative electrode material using sludge as precursor, its preparation method specifically includes following step
Suddenly：
(1) dewatered sludge, digested sludge and humus sludge are ground after cold dry-cure 55h at temperature is for -40 DEG C, then is put
In tube furnace, and under the protection of nitrogen, pre- carbonization treatment 24h under conditions of being 500 DEG C in temperature obtains pre- carbonization and produces
Thing；
(2) after pre- carbonized product is ground, it is placed in hydrofluoric acid, and stirs 1h, washs afterwards and dry, wherein, hydrogen fluorine
The weight/mass percentage composition of hydrogen fluoride is 40% in acid, and pre- carbonized product is 1 with the mass ratio of hydrofluoric acid:0.1；
(3) and then again it is placed in sodium hydrate aqueous solution, and stirs 12h, dries afterwards and grind, wherein, NaOH
The weight/mass percentage composition of NaOH is 18% in the aqueous solution, and NaOH is with the mass ratio of pre- carbonized product in step (2)
1:5；
(4) it is placed in tube furnace, and under the protection of nitrogen, secondary carbonization treatment under conditions of being 1000 DEG C in temperature
1h, obtains secondary carbonized product；
(5) by secondary carbonized product be placed in watery hydrochloric acid soak 10 days, it is scrubbed, drying after, that is, obtain using sludge as
The carbon-based lithium ion cell negative electrode material of precursor, wherein, the weight/mass percentage composition of HCl is 4%, secondary carbonized product in watery hydrochloric acid
It is 1 with the mass ratio of watery hydrochloric acid:10.
The above-mentioned description to embodiment is to be understood that and use invention for ease of those skilled in the art.
Person skilled in the art obviously can easily make various modifications to these embodiments, and described herein general
Principle is applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to above-described embodiment, ability
Field technique personnel announcement of the invention, does not depart from improvement that scope made and modification all should be of the invention
Within protection domain.
Claims (9)
1. a kind of preparation method of carbon-based lithium ion cell negative electrode material using sludge as precursor, it is characterised in that the method
Specifically include following steps：
(1) will be placed in tube furnace after sludge pretreatment, and pre- carbonization treatment is carried out under the protection of inert gas, obtain pre- carbon
Change product；
(2) after pre- carbonized product is ground, it is placed in hydrofluoric acid, and stirs 1-24h, washs afterwards and dry；
(3) and then again it is placed in alkaline solution, and stirs 1-24h, dries afterwards and grind；
(4) it is placed in tube furnace, and secondary carbonization treatment is carried out under the protection of inert gas, obtains secondary carbonized product；
(5) by secondary carbonized product be placed in watery hydrochloric acid soak 1-20 days, it is scrubbed, drying after, that is, obtain described in sludge
As the carbon-based lithium ion cell negative electrode material of precursor.
2. the preparation side of a kind of carbon-based lithium ion cell negative electrode material using sludge as precursor according to claim 1
Method, it is characterised in that in step (1), described sludge includes primary sludge, excess sludge, dewatered sludge, digested sludge or corruption
Grow one or more in sludge.
3. the preparation side of a kind of carbon-based lithium ion cell negative electrode material using sludge as precursor according to claim 1
Method, it is characterised in that in step (1), described preprocessing process is：Sludge is ground after cold dry-cure, it is described
The temperature of cold dry-cure is -50 DEG C to -30 DEG C, and the time is 1-96h.
4. the preparation side of a kind of carbon-based lithium ion cell negative electrode material using sludge as precursor according to claim 1
Method, it is characterised in that in step (1) and step (4), described inert gas is nitrogen or argon gas.
5. the preparation side of a kind of carbon-based lithium ion cell negative electrode material using sludge as precursor according to claim 1
Method, it is characterised in that in step (1), the temperature of described pre- carbonization treatment is 400-600 DEG C, and the time is 1-48h；Step (4)
In, the temperature of described secondary carbonization treatment is 700-1000 DEG C, and the time is 1-48h.
6. the preparation side of a kind of carbon-based lithium ion cell negative electrode material using sludge as precursor according to claim 1
Method, it is characterised in that in step (2), the weight/mass percentage composition of hydrogen fluoride is 0.5-40% in described hydrofluoric acid, and described is pre-
Carbonized product is 1 with the mass ratio of hydrofluoric acid:0.1-10.
7. the preparation side of a kind of carbon-based lithium ion cell negative electrode material using sludge as precursor according to claim 1
Method, it is characterised in that in step (3), described alkaline solution is potassium hydroxide aqueous solution, hydrogen-oxygen in the potassium hydroxide aqueous solution
The weight/mass percentage composition for changing potassium is 5-30%, the mass ratio of the pre- carbonized product described in described potassium hydroxide and step (2)
It is 1:1-10.
8. the preparation side of a kind of carbon-based lithium ion cell negative electrode material using sludge as precursor according to claim 1
Method, it is characterised in that in step (5), the weight/mass percentage composition of HCl is 0.5-10% in described watery hydrochloric acid, and described is secondary
Carbonized product is 1 with the mass ratio of watery hydrochloric acid:1-20.
9. the carbon-based lithium using sludge as precursor that a kind of method used as described in any one of claim 1 to 8 is prepared from
Ion battery cathode material.
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| CN109103530A (en) * | 2018-05-02 | 2018-12-28 | 石河子大学 | A kind of method and carbon material preparing Fe2O3 doping carbon material using discarded wadding body |
| CN110937590A (en) * | 2019-12-19 | 2020-03-31 | 中冶京诚工程技术有限公司 | Preparation method of porous carbon material and prepared porous carbon material |
| CN114132916A (en) * | 2021-12-09 | 2022-03-04 | 泉州师范学院 | Method for preparing metal ion battery negative electrode material by using livestock and poultry manure organic fertilizer |
| CN114188524A (en) * | 2021-12-09 | 2022-03-15 | 泉州师范学院 | Method for preparing microelement-doped silicon-carbon negative electrode material from sludge |
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| CN109103530A (en) * | 2018-05-02 | 2018-12-28 | 石河子大学 | A kind of method and carbon material preparing Fe2O3 doping carbon material using discarded wadding body |
| CN109103530B (en) * | 2018-05-02 | 2020-09-15 | 石河子大学 | Method for preparing iron-doped carbon material by using waste flocs and carbon material |
| CN110937590A (en) * | 2019-12-19 | 2020-03-31 | 中冶京诚工程技术有限公司 | Preparation method of porous carbon material and prepared porous carbon material |
| CN114132916A (en) * | 2021-12-09 | 2022-03-04 | 泉州师范学院 | Method for preparing metal ion battery negative electrode material by using livestock and poultry manure organic fertilizer |
| CN114188524A (en) * | 2021-12-09 | 2022-03-15 | 泉州师范学院 | Method for preparing microelement-doped silicon-carbon negative electrode material from sludge |
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