CN107739031A - A kind of method that lithium ion carbon negative pole material is prepared with bacteria residue waste material - Google Patents

A kind of method that lithium ion carbon negative pole material is prepared with bacteria residue waste material Download PDF

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CN107739031A
CN107739031A CN201710971891.9A CN201710971891A CN107739031A CN 107739031 A CN107739031 A CN 107739031A CN 201710971891 A CN201710971891 A CN 201710971891A CN 107739031 A CN107739031 A CN 107739031A
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bacteria residue
lithium ion
negative pole
mixture
prepared
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CN107739031B (en
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唐晶晶
周向阳
廖群超
杨娟
李晨
蒋敏
王倩
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Dali Chenyu Energy Storage New Material Co ltd
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Central South University
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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 method of multi-element doping level hole carbon is prepared using bacteria residue waste material as raw material the present invention relates to a kind of, and is applied to lithium cell cathode material.Step includes：After the drying of single bacteria residue waste material, ball milling, with metal salt and inorganic base mix and high-temperature calcination is handled, then remove metal impurities with inorganic acid, obtain the level hole carbon of multi-element doping.The level hole carbon that the present invention is prepared has multi-element doping, while abundant micropore, mesoporous and macropore be present, particularly suitable for ion cathode material lithium.Raw material sources of the present invention extensively, technique is simple and convenient to operate, cost is low, products obtained therefrom function admirable, be easily enlarged metaplasia production.

Description

A kind of method that lithium ion carbon negative pole material is prepared with bacteria residue waste material
Technical field
The present invention relates to field of lithium ion battery, more particularly to one kind to prepare lithium ion battery as raw material using bacteria residue waste material and use The method of carbon negative pole material.
Background technology
Lithium ion battery as a kind of green energy storage device, have energy density is big, open-circuit voltage is high, green etc. one The advantage of series, has been widely used in mobile electronic device, such as mobile phone, notebook, portable cameras etc..Graphite Class carbon material is the main commercialization negative material of current lithium ion battery, but the theoretical specific capacity due to graphite in itself only has 372mAh g-1, it is difficult to meet the needs of following high-energy-density.There are some researches show, the porous and element doping of carbon material, energy More avtive spots enough are provided for lithium ion, so as to effectively improve the reversible specific capacity of carbonaceous material.Chinese patent CN 104332596 report and use melamine, phthalaldehyde, CNT and dimethyl sulfoxide (DMSO) as raw material, at Vacuum Heat Reason method, prepare porous carbon/carbon nano tube compound material of N doping.Huawei Song et al. using organic matter as presoma, Using template, porous carbon (Acs Applied Materials＆Interfaces, 2014,6 (23) of N doping are prepared: 21661-8.).When above material is as lithium ion battery negative material, higher specific capacity is shown.However, existing skill In art, preparing the porous carbon materials of element doping, to usually require special carbon source and doped chemical presoma be raw material so that into This costliness, complex operation, limit its use in large-scale production.
Antibiotic bacterium dregs are accompanied by antibiotics production and a kind of caused waste material, including terramycin bacteria residue, penicillin bacterium Slag, cephalosporin dreg etc., its main component are crude protein, crude fat, crude fibre, amino acid etc., containing substantial amounts of carbon, nitrogen, Oxygen element and a small amount of metallic element, such as calcium, iron, zinc, magnesium.China is antibiotic big country, and substantial amounts of bacterium is produced per annual meeting Slag waste material.In order to prevent its bulk deposition, the measure burned and buried mainly is taken to handle, but flue dust meeting caused by burning Air is polluted, burial makes it be dissolved in underground water, causes water pollution.Above two processing method is also the wave to " resource " simultaneously Take.How effectively and reasonably to handle these bacteria residue waste materials turns into the problem of urgently handling at present.In fact, bacteria residue due to containing More than 40% carbon component, it is suitable for obtaining the carbon material with certain function by calcining, and contains in bacteria residue certain The elements such as the nitrogen of ratio, phosphorus, can be directly as the source beneficial to doped chemical.Up to the present, using bacteria residue waste material as raw material The correlation technique for preparing lithium ion carbon negative pole material is also rarely reported.
The content of the invention
Present invention is primarily intended to solve the problems, such as current technology, there is provided a kind of simple method, using bacteria residue waste material as original Material, the level hole carbon with multi-element doping is prepared as lithium ion battery negative material.
A kind of method that lithium ion carbon negative pole material is prepared with bacteria residue waste material of the present invention, comprises the steps；
Step 1
Dry bacteria residue powder is well mixed with metal salt and inorganic base, obtains mixture；In the mixture, dry Bacteria residue powder, metal salt, inorganic base mass ratio be 15~2:1:1~8；The bacteria residue powder is selected from terramycin strain ground-slag One kind in end, cephalosporin dreg powder, penicillin mushroom dregs powder；
Step 2
Under protective atmosphere, high-temperature calcination is carried out to mixture obtained by step 1；Mixture after being carbonized；The height The temperature of temperature calcining is 700~1100 DEG C；
Step 3
Mixture after being carbonized obtained by step 2 is placed in the solution containing inorganic acid after soaking at least 6h, filtering, obtained Filter residue, filter residue is cleaned, until the pH most 6-8 of washing lotion；Obtain semi-finished product；After gained semi-finished product drying, obtain having polynary The level hole carbon negative pole material of element doping, that is, obtain described lithium ion carbon negative pole material.
A kind of method that lithium ion carbon negative pole material is prepared with bacteria residue waste material of the present invention, in the bacteria residue powder of the drying, Carbon content in 20~50wt%, nitrogen content in 5~15wt%, oxygen content in 10~30wt%, phosphorus content in 0.1~15wt%, Sulfur content is in 0.1~15wt%；
A kind of method that lithium ion carbon negative pole material is prepared with bacteria residue waste material of the present invention, the bacteria residue powder of the drying is logical Cross following proposal preparation：
Bacteria residue waste material is placed in 12~36h of baking in 80~120 DEG C of vacuum drying chamber, removes the water in bacteria residue waste material Point, then by dry bacteria residue waste material 6~12h of ball milling, obtain dry bacteria residue powder；The particle diameter of the bacteria residue powder of the drying For 5-50 μm.
A kind of method that lithium ion carbon negative pole material is prepared with bacteria residue waste material of the present invention, in the mixture, dry bacterium Ground-slag end, metal salt, the mass ratio of inorganic base are 10~3:1:1~8.
A kind of method that lithium ion carbon negative pole material is prepared with bacteria residue waste material of the present invention, when bacteria residue powder is terramycin bacteria residue During powder, in the mixture, dry bacteria residue powder, metal salt, the mass ratio of inorganic base are 10~3:1:1~5.As entering The preferred scheme of one step, in the mixture, dry bacteria residue powder, metal salt, the mass ratio of inorganic base are 7~5:1:2~ 4.As most preferably scheme, in the mixture, dry bacteria residue powder, metal salt, the mass ratio of inorganic base are 6:1:3.
The present invention is a kind of to prepare the method for lithium ion carbon negative pole material when bacteria residue powder is penicillin mushroom dregs using bacteria residue waste material During powder, in the mixture, dry bacteria residue powder, metal salt, the mass ratio of inorganic base are 15~7:2:2~11.As Further preferred scheme, in the mixture, dry bacteria residue powder, metal salt, the mass ratio of inorganic base are 13~5:2~ 1:4~6.As most preferably scheme, in the mixture, dry bacteria residue powder, metal salt, the mass ratio of inorganic base are 11: 2:6。
The present invention is a kind of to prepare the method for lithium ion carbon negative pole material when bacteria residue powder is Cephalosporin slag using bacteria residue waste material During powder, in the mixture, dry bacteria residue powder, metal salt, the mass ratio of inorganic base are 20~6:2:3~15.As Further preferred scheme, in the mixture, dry bacteria residue powder, metal salt, the mass ratio of inorganic base are 15~9:2:5 ~10.As most preferably scheme, in the mixture, dry bacteria residue powder, metal salt, the mass ratio of inorganic base are 12:2: 7。
A kind of method that lithium ion carbon negative pole material is prepared with bacteria residue waste material of the present invention, in step 1, distributed by setting group After taking dry bacteria residue powder, metal salt, inorganic base, it will be placed in water with the drying bacteria residue powder, metal salt, the inorganic base that take, After stirring, 80~100 DEG C are warming up to, is stirred continuously until that moisture is evaporated；Obtain the mixture；The stirring is magnetic force Stirring, the rotating speed of magnetic agitation is 300~1000rmin-1。
A kind of method that lithium ion carbon negative pole material is prepared with bacteria residue waste material of the present invention, the metal salt is water-soluble metal Salt, and cation is selected from least one of iron, copper, zinc, nickel, cobalt, manganese；The inorganic base is sodium hydroxide, potassium hydroxide It is one or two kinds of.Preferably, the metal salt be selected from iron, copper, zinc, nickel, cobalt, at least one of manganese chlorate and/ Or nitrate.
A kind of method that lithium ion carbon negative pole material is prepared with bacteria residue waste material of the present invention, in step 2, under protective atmosphere, 1~5h of high-temperature calcination is carried out to mixture obtained by step 1；Mixture after being carbonized；The temperature of the high-temperature calcination is 700~1100 DEG C.
Preferably, a kind of method that lithium ion carbon negative pole material is prepared with bacteria residue waste material of the present invention, in step 2, Under protective atmosphere, 1~5h of high-temperature calcination is carried out to mixture obtained by step 1；Mixture after being carbonized；The high temperature The temperature of calcining is 700~1100 DEG C；The protective atmosphere in nitrogen atmosphere, argon gas atmosphere, hydrogen-argon-mixed atmosphere extremely Few one kind, during high-temperature calcination, the flow velocity of protective gas is 0.2~2L/min.In industrial applications, using 1~10 DEG C/min Heating rate, from room temperature to 700~1100 DEG C, be preferably 980~1050 DEG C, more preferably 1000 DEG C.
A kind of method that lithium ion carbon negative pole material is prepared with bacteria residue waste material of the present invention, in step 2, the protective atmosphere Selected from least one of nitrogen atmosphere, argon gas atmosphere, hydrogen-argon-mixed atmosphere, during high-temperature calcination, the flow velocity of protective gas is 0.2 ~2L/min.
A kind of method that lithium ion carbon negative pole material is prepared with bacteria residue waste material of the present invention, in step 3, inorganic acid is hydrochloric acid And/or sulfuric acid；In the solution containing inorganic acid；The concentration of inorganic acid is 0.1~3mol/L.
Preferably, a kind of method that lithium ion carbon negative pole material is prepared with bacteria residue waste material of the present invention, in step 3, Inorganic acid is hydrochloric acid and/or sulfuric acid；In the solution containing inorganic acid, the concentration of inorganic acid is 0.1~3mol/L.
A kind of method that lithium ion carbon negative pole material is prepared with bacteria residue waste material of the present invention, in step 3, by obtained by step 2 Mixture after carbonization is placed in the solution containing inorganic acid, after 6~12h of stirring immersion, filtering, is obtained filter residue, is cleaned filter residue, directly To the pH most 6~8 of washing lotion；Obtain semi-finished product；Gained semi-finished product are obtained with multi-element doping after 60~100 DEG C of drying Level hole carbon negative pole material, that is, obtain described lithium ion carbon negative pole material.
Preferably, a kind of method that lithium ion carbon negative pole material is prepared with bacteria residue waste material of the present invention, in step 3, In the level hole carbon negative pole material with multi-element doping, doped chemical includes the one or more in nitrogen, oxygen, phosphorus, sulphur. As further preferred scheme, in the level hole carbon negative pole material with multi-element doping the content of nitrogen be 0.1~ 10wt%, the content of oxygen is 0.1~10wt%, and the content of phosphorus is 0.1~10wt%, and the content of sulphur is 0.1~10wt%.
A kind of method that lithium ion carbon negative pole material is prepared with bacteria residue waste material of the present invention, described lithium ion Carbon anode material Material, when current density is 0.1A/g, its first discharge specific capacity is 812~1194mAh/g, and after 100 circulations, it can Inverse capacity remains in that 682~982mAh/g.After optimized, its first discharge specific capacity is 900~1194mAh/g, by 100 After secondary circulation, its reversible capacity remains in that 730~982mAh/g.
The principle of the present invention is：Bacteria residue waste material contains the elements such as substantial amounts of carbon, nitrogen, oxygen, phosphorus, sulphur, in protective atmosphere Under, by 700~1100 DEG C of calcining, carbon therein carbonizes, and nitrogen, oxygen, phosphorus, sulphur can adulterate form part and stay Deposit, so as to obtain the carbon material of multi-element doping.In addition, appropriate inorganic base reacts during high-temperature calcination with carbon material, Carbon material is set to produce substantial amounts of hole, including macropore, mesoporous and micropore.At the same time, appropriate metal salt is in high-temperature calcination During can also be reacted with carbon, generate metal simple-substance and carbon dioxide, make further to be formed in carbon material substantial amounts of micropore and It is mesoporous, and the metal simple-substance generated has the function that catalyzed graphitization, is remarkably improved the orderly journey of atomic arrangement of bacteria residue carbon Degree, so as to improve conductance.Mass ratio of the invention by controlling dry bacteria residue powder, metal salt, inorganic base, at other Under the synergy of part parameter, obtain that there is rational pore-size distribution and high conductive multi-element doping level hole carbon, should When multi-element doping level hole carbon is applied to lithium ion battery negative material, excellent electric property is shown.The present invention's is beneficial Effect：
(1) the bacteria residue waste material in the present invention as the raw material for preparing multi-element doping level hole carbon, wide material sources, belongs to pharmacy The solid waste of industry, it is in need of immediate treatment and reluctant harmful substance, the present invention is by such solid waste by simply having The technical scheme of effect, the new energy materialses with high added value are prepared into, there is very high economic benefit and social benefit.
(2) present invention prepares bacteria residue waste material used in the carbon of multi-element doping level hole in itself containing a certain amount of nitrogen, oxygen, sulphur, phosphorus Deng element, therefore, there is no need to add dopant doping in addition.Element doping can not only improve carbon material storage lithium ability, while Can be as the avtive spot of storage lithium, so as to largely improve the reversible specific capacity of carbon material.
(3) during the present invention prepares multi-element doping level hole carbon, while using appropriate inorganic base and metal salt to carbon Material carries out pore-creating, so as to get carbon material there is abundant and rational micropore, mesoporous and macropore, wherein, micropore can provide The avtive spot of more lithium ions, the mesoporous transmission range for being advantageous to shorten lithium ion, macropore can accommodate substantial amounts of electrolyte. In addition, the metal simple-substance obtained by appropriate metal salt and carbon material reaction can play catalytic graphite to carbon material at high temperature Change acts on, and improves the atomic arrangement order degree of carbon material, so as to improve its conductance, thus improves negative material from many aspects Comprehensive electrochemical.
(4) present invention process is simple, easy to operate, green, cost is cheap, and yield is high, it is easy to accomplish extensive raw Production.
Brief description of the drawings：
Fig. 1 is the scanning electron microscope (SEM) photograph of multi-element doping level hole carbon prepared by the embodiment of the present invention 1.
Fig. 2 is the isothermal nitrogen adsorption desorption curve of multi-element doping level hole carbon prepared by the embodiment of the present invention 1.
Fig. 3 is the x-ray photoelectron energy spectrum diagram of multi-element doping level hole carbon prepared by the embodiment of the present invention 1.
Fig. 4 is the cyclic curve of the battery of the multi-element doping level hole carbon material assembling prepared by the embodiment of the present invention 1 Figure.
It will be seen from figure 1 that the material prepared has obvious porous laminated structure.
Figure it is seen that the material prepared while there is micropore, mesoporous, macropore level hole characteristic.
From figure 3, it can be seen that the material prepared mainly is made up of tri- kinds of elements of C, N, O.
From fig. 4, it can be seen that show to possess when the material prepared of the present invention is as negative electrode of lithium ion battery it is high can Inverse specific capacity and outstanding cycle performance.
Embodiment
With reference to example, the present invention is described further, but the implementation of the present invention is not limited to this.
In the embodiment of the present invention and comparative example, in the terramycin of drying used, carbon content 40wt%, nitrogen content exists 9wt%, oxygen content is in 32wt%, and phosphorus content is in 1.2wt%, and sulfur content is in 0.8wt%.
In dry penicillin mushroom dregs used, carbon content 43wt%, nitrogen content contains in 9wt%, oxygen content in 35wt%, phosphorus Measure in 1.1wt%, sulfur content is in 1.5wt%.
In Cephalosporin slag bacteria residue used, carbon content 44wt%, nitrogen content is in 11wt%, and oxygen content is in 37wt%, phosphorus Content is in 0.7wt%, and sulfur content is in 1.1wt%.
Embodiment 1
(1) terramycin bacteria residue is placed in 100 DEG C of vacuum drying chamber and toasts 24h, remove moisture, it is then dry by what is obtained Dry bacteria residue waste material ball milling 6h, obtain the bacteria residue powder (2) that average grain diameter is about 20 microns and take gained in a certain amount of step (1) Terramycin bacteria residue and nickel chloride and sodium hydroxide in mass ratio 10:1:1 ratio mixes in aqueous, and continues at 80 DEG C Stirring is evaporated up to moisture, obtains the homogeneous mixture of nickel chloride, nickel hydroxide, sodium hydroxide and bacteria residue；
(3) homogeneous mixture for nickel chloride, nickel hydroxide, sodium hydroxide and the bacteria residue for obtaining step (2) is in nitrogen gas 1000 DEG C of high temperature are risen to, are incubated 2h with 1L/min air velocity, 5 DEG C/min heating rate under atmosphere, obtain containing nickel, chlorine Change the mixture of sodium and level hole carbon；(4) mixture containing nickel, sodium chloride and level hole carbon of gained in step (3) is soaked Stain after stirring 6h, is filtered by vacuum and is washed with deionized to PH=7 in the hydrochloric acid solution that molar concentration is 1mol/L；
(5) filter cake of gained in step (4) is dried at 80 DEG C, finally gives the level hole Carbon anode material of multi-element doping Material.
For the multi-element doping level hole carbon lithium ion negative material that the method obtains when current density is 0.1A/g, it is first Specific discharge capacity is 909mAh/g, and coulombic efficiency is 74.3% first, and after 100 circulations, its reversible capacity remains in that In 712mAh/g.
Embodiment 2
(1) terramycin bacteria residue is placed in 100 DEG C of vacuum drying chamber and toasts 24h, remove moisture, it is then dry by what is obtained Dry bacteria residue waste material ball milling 6h, obtain the soil that the bacteria residue powder (2) that average grain diameter is about 20 μm takes gained in a certain amount of step (1) Mycin bacteria residue and nickel chloride and sodium hydroxide in mass ratio 6:1:3 ratio mixes in aqueous, and is persistently stirred at 80 DEG C Mix until moisture be evaporated, obtain the homogeneous mixture of nickel chloride, nickel hydroxide, sodium hydroxide and bacteria residue；
(3) homogeneous mixture for nickel chloride, nickel hydroxide, sodium hydroxide and the bacteria residue for obtaining step (2) is in nitrogen gas 1000 DEG C of high temperature are risen to, are incubated 2h with 1L/min air velocity, 5 DEG C/min heating rate under atmosphere, obtain containing nickel, chlorine Change the mixture of sodium and level hole carbon；(4) mixture containing nickel, sodium chloride and level hole carbon of gained in step (3) is soaked Stain after stirring 6h, is filtered by vacuum and is washed with deionized to PH=7 in the hydrochloric acid solution that molar concentration is 1mol/L；
(5) filter cake of gained in step (4) is dried at 80 DEG C, finally gives the level hole Carbon anode material of multi-element doping Material.
The multi-element doping level hole carbon lithium ion negative material that the method obtains possesses higher specific capacity and preferable times Rate performance, when current density is 0.1A/g, its first discharge specific capacity is 1169mAh/g, and coulombic efficiency is 79.3% first, After 100 circulations, its reversible capacity stills remain in 960mAh/g.
Embodiment 3
(1) terramycin bacteria residue is placed in 100 DEG C of vacuum drying chamber and toasts 24h, remove moisture, it is then dry by what is obtained Dry bacteria residue waste material ball milling 6h, obtain the soil that the bacteria residue powder (2) that average grain diameter is about 20 μm takes gained in a certain amount of step (1) Mycin bacteria residue and nickel chloride and sodium hydroxide in mass ratio 3:1:5 ratio mixes in aqueous, and is persistently stirred at 80 DEG C Mix until moisture be evaporated, obtain the homogeneous mixture of nickel chloride, nickel hydroxide, sodium hydroxide and bacteria residue；
(3) homogeneous mixture for nickel chloride, nickel hydroxide, sodium hydroxide and the bacteria residue for obtaining step (2) is in nitrogen gas Under atmosphere, with 1L/min air velocity, 5 DEG C/min heating rate rises to 1000 DEG C of high temperature, is incubated 2h, obtains containing nickel, chlorine Change the mixture of sodium and level hole carbon；
(4) it is in molar concentration by the impregnation mixture containing nickel, sodium chloride and level hole carbon of gained in step (3) In 1mol/L hydrochloric acid solution, after stirring 6h, it is filtered by vacuum and is washed with deionized to PH=7；
(5) filter cake of gained in step (4) is dried at 80 DEG C, finally gives the level hole Carbon anode material of multi-element doping Material.
For the multi-element doping level hole carbon lithium ion negative material that the method obtains when current density is 0.1A/g, it is first Specific discharge capacity is 944mAh/g, and coulombic efficiency is 68.3% first, and after 100 circulations, its reversible capacity remains in that In 782mAh/g.
By embodiment 1,2,3 as can be seen that using preferred scheme of the invention, its products obtained therefrom performance is significantly carried Rise.
Comparative example 1
(1) terramycin bacteria residue is placed in 100 DEG C of vacuum drying chamber and toasts 24h, remove moisture, it is then dry by what is obtained Dry bacteria residue waste material ball milling 6h, obtain the soil that the bacteria residue powder (2) that average grain diameter is about 20 μm takes gained in a certain amount of step (1) Mycin bacteria residue and nickel chloride in mass ratio 6:1 ratio mixes in aqueous, and is stirred continuously until that moisture steams at 80 DEG C It is dry, obtain the homogeneous mixture of nickel chloride and bacteria residue；
(3) nickel chloride and the homogeneous mixture of bacteria residue obtained step (2) in a nitrogen atmosphere, with 1L/min air-flow Speed, 5 DEG C/min heating rate rise to 1000 DEG C of high temperature, are incubated 2h, obtain the mixture containing metallic nickel Yu level hole carbon；
(4) by the impregnation mixture containing metallic nickel and level hole carbon of gained in step (3) in molar concentration be 1mol/ In L hydrochloric acid solution, after stirring 6h, it is filtered by vacuum and is washed with deionized to PH=7；
(5) filter cake of gained in step (4) is dried at 80 DEG C, finally gives the level hole Carbon anode material of multi-element doping Material.
For the multi-element doping level hole carbon lithium ion negative material that the method obtains when current density is 0.1A/g, it is first Specific discharge capacity is 529mAh/g, and coulombic efficiency is 65.6% first, and after 100 circulations, its reversible capacity only has 422mAh/g。
By embodiment 1,2,3 and comparative example 1 as can be seen that when not adding alkali in activation pore creating material, its products obtained therefrom Performance is much worse than the scheme designed by the present invention.
Comparative example 2
(1) terramycin bacteria residue is placed in 100 DEG C of vacuum drying chamber and toasts 24h, remove moisture, it is then dry by what is obtained Dry bacteria residue waste material ball milling 6h, obtain the soil that the bacteria residue powder (2) that average grain diameter is about 20 μm takes gained in a certain amount of step (1) Mycin bacteria residue and sodium hydroxide in mass ratio 2:1 ratio mixes in aqueous, and is stirred continuously until moisture at 80 DEG C It is evaporated, obtains the homogeneous mixture of sodium hydroxide and bacteria residue；
(3) sodium hydroxide and the homogeneous mixture of bacteria residue obtained step (2) in a nitrogen atmosphere, with 1L/min gas Flow velocity degree, 5 DEG C/min heating rate rise to 1000 DEG C of high temperature, are incubated 2h, obtain the mixing containing sodium carbonate Yu level hole carbon Thing；
(4) by the impregnation mixture containing sodium carbonate and level hole carbon of gained in step (3) in molar concentration be 1mol/ In L hydrochloric acid solution, after stirring 6h, it is filtered by vacuum and is washed with deionized to neutrality；
(5) filter cake of gained in step (4) is dried at 80 DEG C, finally gives the level hole Carbon anode material of multi-element doping Material.
The multi-element doping level hole carbon lithium ion negative material that the method obtains possesses higher specific capacity and preferable times Rate performance, when current density is 0.1A/g, its first discharge specific capacity is 721mAh/g, and coulombic efficiency is 63.3% first, After 100 circulations, its reversible capacity is maintained at 582mAh/g.
By embodiment 1,2,3 and comparative example 2 as can be seen that not adding nickel chloride (i.e. metal salt) in activation pore creating material When, the performance of its products obtained therefrom is much worse than the scheme designed by the present invention.
Comparative example 3
The uniform embodiment 3 of other conditions is consistent, and difference is：The matter of terramycin bacteria residue and nickel chloride and sodium hydroxide Amount is than being 20:1:1；For its products obtained therefrom when current density is 0.1A/g, its first discharge specific capacity is only 432mAh/g, first Coulombic efficiency is 55.9%, and after 100 circulations, its reversible capacity only has 209mAh/g.
Comparative example 4
The uniform embodiment 3 of other conditions is consistent, and difference is：The matter of terramycin bacteria residue and nickel chloride and sodium hydroxide Amount is than being 2:1:5；For its products obtained therefrom when current density is 0.1A/g, its first discharge specific capacity is only 478mAh/g, first Coulombic efficiency is 42.8%, and after 100 circulations, its reversible capacity only has 187mAh/g.
By embodiment 1,2,3 and comparative example 4,5 as can be seen that not using the design of the present invention, its products obtained therefrom Performance is decreased obviously.
Embodiment 4
1) penicillin mushroom dregs are placed in 100 DEG C of vacuum drying chamber and toast 24h, remove moisture, it is then dry by what is obtained Dry bacteria residue waste material ball milling 6h, obtains the bacteria residue powder that average grain diameter is about 25 μm；
(2) the terramycin bacteria residue of gained and nickel chloride and sodium hydroxide in mass ratio 15 in a certain amount of step (1) are taken:2:2 Ratio mix in aqueous, and be stirred continuously until that moisture is evaporated at 80 DEG C, obtain nickel chloride, nickel hydroxide, hydrogen-oxygen Change the homogeneous mixture of sodium and bacteria residue；
(3) homogeneous mixture for nickel chloride, nickel hydroxide, sodium hydroxide and the bacteria residue for obtaining step (2) is in nitrogen gas Under atmosphere, with 1L/min air velocity, 5 DEG C/min heating rate rises to 1000 DEG C of high temperature, is incubated 2h, obtains containing nickel, chlorine Change the mixture of sodium and level hole carbon；
(4) it is in molar concentration by the impregnation mixture containing nickel, sodium chloride and level hole carbon of gained in step (3) In 1mol/L hydrochloric acid solution, 6h is stirred, is filtered by vacuum and is washed with deionized to PH=7；
(5) filter cake of gained in step (4) is dried at 80 DEG C, finally gives the level hole Carbon anode material of multi-element doping Material.
The multi-element doping level hole carbon lithium ion negative material that the method obtains possesses higher specific capacity and preferable times Rate performance, when current density is 0.1A/g, its first discharge specific capacity is 954mAh/g, and coulombic efficiency is 68.3% first, After 100 circulations, its reversible capacity stills remain in 732mAh/g.
Embodiment 5
1) penicillin mushroom dregs are placed in 100 DEG C of vacuum drying chamber and toast 24h, remove moisture, it is then dry by what is obtained Dry bacteria residue waste material ball milling 6h, obtains the bacteria residue powder that average grain diameter is about 25 μm；
(2) the terramycin bacteria residue of gained and nickel chloride and sodium hydroxide in mass ratio 7 in a certain amount of step (1) are taken:2:11 Ratio mix in aqueous, and be stirred continuously until that moisture is evaporated at 80 DEG C, obtain nickel chloride, nickel hydroxide, hydrogen-oxygen Change the homogeneous mixture of sodium and bacteria residue；
(3) homogeneous mixture for nickel chloride, nickel hydroxide, sodium hydroxide and the bacteria residue for obtaining step (2) is in nitrogen gas Under atmosphere, with 1L/min air velocity, 5 DEG C/min heating rate rises to 1000 DEG C of high temperature, is incubated 2h, obtains containing nickel, chlorine Change the mixture of sodium and level hole carbon；；
(4) it is in molar concentration by the impregnation mixture containing nickel, sodium chloride and level hole carbon of gained in step (3) In 1mol/L hydrochloric acid solution, 6h is stirred, is filtered by vacuum and is washed with deionized to PH=7；
(5) filter cake of gained in step (4) is dried at 80 DEG C, finally gives the level hole Carbon anode material of multi-element doping Material.
The multi-element doping level hole carbon lithium ion negative material that the method obtains possesses higher specific capacity and preferable times Rate performance, when current density is 0.1A/g, its first discharge specific capacity is 912mAh/g, and coulombic efficiency is 70.3% first, After 100 circulations, its reversible capacity stills remain in 782mAh/g.
Embodiment 6
(1) penicillin mushroom dregs are placed in 100 DEG C of vacuum drying chamber and toast 24h, remove moisture, it is then dry by what is obtained Dry bacteria residue waste material ball milling 6h, obtains the bacteria residue powder that particle mean size is about 25 microns；
(2) the terramycin bacteria residue of gained and nickel chloride and sodium hydroxide in mass ratio 11 in a certain amount of step (1) are taken:2:6 Ratio mix in aqueous, and be stirred continuously until that moisture is evaporated at 80 DEG C, obtain nickel chloride, nickel hydroxide, hydrogen-oxygen Change the homogeneous mixture of sodium and bacteria residue；
(3) homogeneous mixture for nickel chloride, nickel hydroxide, sodium hydroxide and the bacteria residue for obtaining step (2) is in nitrogen gas Under atmosphere, with 1L/min air velocity, 5 DEG C/min heating rate rises to 1000 DEG C of high temperature, is incubated 2h, obtains containing nickel, chlorine Change the mixture of sodium and level hole carbon；
(4) it is in molar concentration by the impregnation mixture containing nickel, sodium chloride and level hole carbon of gained in step (3) In 1mol/L hydrochloric acid solution, 6h is stirred, is filtered by vacuum and is washed with deionized to PH=7；
(5) filter cake of gained in step (4) is dried at 80 DEG C, finally gives the level hole Carbon anode material of multi-element doping Material.
For the multi-element doping level hole carbon lithium ion negative material that the method obtains when current density is 0.1A/g, it is first Specific discharge capacity is 1194mAh/g, and coulombic efficiency is 78.3% first, and after 100 circulations, its reversible capacity is maintained at 982mAh/g。
Contrasted by the inherence of embodiment 4,5,6, it can be seen that using the preferred scheme of the present invention, its products obtained therefrom It can be significantly improved.
Embodiment 7
(1) Cephalosporin slag is placed in 100 DEG C of vacuum drying chamber and toasts 24h, remove moisture, it is then dry by what is obtained Dry bacteria residue waste material ball milling 6h, obtains the bacteria residue powder that particle mean size is about 30 μm；
(2) the terramycin bacteria residue of gained and nickel chloride and sodium hydroxide in mass ratio 20 in a certain amount of step (1) are taken:2:3 Ratio mix in aqueous, and be stirred continuously until that moisture is evaporated at 80 DEG C, obtain nickel chloride, nickel hydroxide, hydrogen-oxygen Change the homogeneous mixture of sodium and bacteria residue；
(3) homogeneous mixture for nickel chloride, nickel hydroxide, sodium hydroxide and the bacteria residue for obtaining step (2) is in nitrogen gas Under atmosphere, with 1L/min air velocity, 5 DEG C/min heating rate rises to 1000 DEG C of high temperature, is incubated 2h, obtains containing nickel, chlorine Change the mixture of sodium and level hole carbon；
(4) it is in molar concentration by the impregnation mixture containing nickel, sodium chloride and level hole carbon of gained in step (3) In 1mol/L hydrochloric acid solution, 6h is stirred, is filtered by vacuum and is washed with deionized to PH=7；
(5) filter cake of gained in step (4) is dried at 80 DEG C, finally gives the level hole Carbon anode material of multi-element doping Material.
For the multi-element doping level hole carbon lithium ion negative material that the method obtains when current density is 0.1A/g, it is first Specific discharge capacity is 864mAh/g, and coulombic efficiency is 68.3% first, and after 100 circulations, its reversible capacity is maintained at 732mAh/g。
Embodiment 8
(1) Cephalosporin slag is placed in 100 DEG C of vacuum drying chamber and toasts 24h, remove moisture, it is then dry by what is obtained Dry bacteria residue waste material ball milling 6h, obtains the bacteria residue powder that particle mean size is about 30 μm；
(2) the terramycin bacteria residue of gained and nickel chloride and sodium hydroxide in mass ratio 6 in a certain amount of step (1) are taken:2:15 Ratio mix in aqueous, and be stirred continuously until that moisture is evaporated at 80 DEG C, obtain nickel chloride, nickel hydroxide, hydrogen-oxygen Change the homogeneous mixture of sodium and bacteria residue；
(3) homogeneous mixture for nickel chloride, nickel hydroxide, sodium hydroxide and the bacteria residue for obtaining step (2) is in nitrogen gas Under atmosphere, with 1L/min air velocity, 5 DEG C/min heating rate rises to 1000 DEG C of high temperature, is incubated 2h, obtains containing nickel, chlorine Change the mixture of sodium and level hole carbon；
(4) it is in molar concentration by the impregnation mixture containing nickel, sodium chloride and level hole carbon of gained in step (3) In 1mol/L hydrochloric acid solution, 6h is stirred, is filtered by vacuum and is washed with deionized to PH=7；
(5) filter cake of gained in step (4) is dried at 80 DEG C, finally gives the level hole Carbon anode material of multi-element doping Material.
For the multi-element doping level hole carbon lithium ion negative material that the method obtains when current density is 0.1A/g, it is first Specific discharge capacity is 812mAh/g, and coulombic efficiency is 62.5% first, and after 100 circulations, its reversible capacity is maintained at 682mAh/g。
Embodiment 9
(1) Cephalosporin slag is placed in 100 DEG C of vacuum drying chamber and toasts 24h, remove moisture, it is then dry by what is obtained Dry bacteria residue waste material ball milling 6h, obtains the bacteria residue powder that particle mean size is about 25 μm；
(2) the terramycin bacteria residue of gained and nickel chloride and sodium hydroxide in mass ratio 12 in a certain amount of step (1) are taken:2:7 Ratio mix in aqueous, and be stirred continuously until that moisture is evaporated at 80 DEG C, obtain nickel chloride, nickel hydroxide, hydrogen-oxygen Change the homogeneous mixture of sodium and bacteria residue；
(3) homogeneous mixture for nickel chloride, nickel hydroxide, sodium hydroxide and the bacteria residue for obtaining step (2) is in nitrogen gas Under atmosphere, with 1L/min air velocity, 5 DEG C/min heating rate rises to 1000 DEG C of high temperature, is incubated 2h, obtains containing nickel, chlorine Change the mixture of sodium and level hole carbon；
(4) it is in molar concentration by the impregnation mixture containing nickel, sodium chloride and level hole carbon of gained in step (3) In 1mol/L hydrochloric acid solution, 6h is stirred, is filtered by vacuum and is washed with deionized to PH=7；
(5) filter cake of gained in step (4) is dried at 80 DEG C, finally gives the level hole Carbon anode material of multi-element doping Material.
For the multi-element doping level hole carbon lithium ion negative material that the method obtains when current density is 0.1A/g, it is first Specific discharge capacity is 1109mAh/g, and coulombic efficiency is 76.2% first, and after 100 circulations, its reversible capacity is maintained at 962mAh/g。
Contrasted by the inherence of embodiment 7,8,9, it can be seen that using the preferred scheme of the present invention, its products obtained therefrom It can be significantly improved.

Claims (10)

  1. A kind of 1. method that lithium ion carbon negative pole material is prepared with bacteria residue waste material, it is characterised in that：Comprise the steps；
    Step 1
    Dry bacteria residue powder is well mixed with metal salt and inorganic base, obtains mixture；In the mixture, dry bacterium Ground-slag end, metal salt, the mass ratio of inorganic base are 15~2:1:1~8；The bacteria residue powder is selected from terramycin strain ground-slag end, head One kind in spore rhzomorph bacteria residue powder, penicillin mushroom dregs powder；
    Step 2
    Under protective atmosphere, high-temperature calcination is carried out to mixture obtained by step 1；Mixture after being carbonized；The high temperature is forged The temperature of burning is 700~1100 DEG C；
    Step 3
    Mixture after being carbonized obtained by step 2 is placed in the solution containing inorganic acid after soaking at least 6h, filtering, obtains filter residue, Filter residue is cleaned, until the pH most 6-8 of washing lotion；Obtain semi-finished product；After gained semi-finished product drying, obtain with multi-element doping Level hole carbon negative pole material, that is, obtain described lithium ion carbon negative pole material.
  2. A kind of 2. method that lithium ion carbon negative pole material is prepared with bacteria residue waste material according to claim 1, it is characterised in that：
    In the bacteria residue powder of the drying, carbon content in 20~50wt%, nitrogen content in 5~15wt%, oxygen content 10~ 30wt%, phosphorus content is in 0.1~15wt%, and sulfur content is in 0.1~15wt%；
    The bacteria residue powder of the drying is prepared by following proposal：
    Bacteria residue waste material is placed in 12~36h of baking in 80~120 DEG C of vacuum drying chamber, removes the moisture in bacteria residue waste material, so Afterwards by dry bacteria residue waste material 6~12h of ball milling, dry bacteria residue powder is obtained；The particle diameter of the bacteria residue powder of the drying is 5- 50μm。
  3. A kind of 3. method that lithium ion carbon negative pole material is prepared with bacteria residue waste material according to claim 1, it is characterised in that： In the mixture, dry bacteria residue powder, metal salt, the mass ratio of inorganic base are 10~3:1:1~8.
  4. A kind of 4. method that lithium ion carbon negative pole material is prepared with bacteria residue waste material according to claim 1, it is characterised in that：
    When bacteria residue powder is terramycin strain ground-slag end, in the mixture, dry bacteria residue powder, metal salt, inorganic base Mass ratio is 10~3:1:1~5；
    When bacteria residue powder is penicillin mushroom dregs powder, in the mixture, dry bacteria residue powder, metal salt, inorganic base Mass ratio is 15~7:2:2~11；
    When bacteria residue powder is Cephalosporin ground-slag end, in the mixture, dry bacteria residue powder, metal salt, inorganic base Mass ratio is 20~6:2:3~15.
  5. A kind of 5. method that lithium ion carbon negative pole material is prepared with bacteria residue waste material according to claim 1, it is characterised in that： In step 1, after taking dry bacteria residue powder, metal salt, inorganic base by the distribution of setting group, by with drying bacteria residue powder, the gold taken Category salt, inorganic base are placed in water, and after stirring, are warming up to 80~100 DEG C, are stirred continuously until that moisture is evaporated；Obtain described Mixture；The stirring is magnetic agitation, and the rotating speed of magnetic agitation is 300~1000rmin-1。
  6. A kind of 6. method that lithium ion carbon negative pole material is prepared with bacteria residue waste material according to claim 1, it is characterised in that：
    The metal salt is water-soluble metal salt, and cation is selected from least one of iron, copper, zinc, nickel, cobalt, manganese；
    The inorganic base is sodium hydroxide, the one or two of potassium hydroxide.
  7. A kind of 7. method that lithium ion carbon negative pole material is prepared with bacteria residue waste material according to claim 1, it is characterised in that： In step 2, under protective atmosphere, 1~5h of high-temperature calcination is carried out to mixture obtained by step 1；Mixture after being carbonized； The temperature of the high-temperature calcination is 700~1100 DEG C.
  8. A kind of 8. method that lithium ion carbon negative pole material is prepared with bacteria residue waste material according to claim 1, it is characterised in that： In step 2, the protective atmosphere is selected from least one of nitrogen atmosphere, argon gas atmosphere, hydrogen-argon-mixed atmosphere, high-temperature calcination When, the flow velocity of protective gas is 0.2~2L/min.
  9. A kind of 9. method that lithium ion carbon negative pole material is prepared with bacteria residue waste material according to claim 1, it is characterised in that：
    In step 3, inorganic acid is hydrochloric acid and/or sulfuric acid；In the solution containing inorganic acid；The concentration of inorganic acid be 0.1~ 3mol/L。
  10. 10. a kind of method that lithium ion carbon negative pole material is prepared with bacteria residue waste material according to claim 1, its feature exist In：In step 3, the mixture after being carbonized obtained by step 2 is placed in the solution containing inorganic acid, after 6~12h of stirring immersion, Filtering, filter residue is obtained, clean filter residue, until the pH most 6~8 of washing lotion；Obtain semi-finished product；Gained semi-finished product are at 60~100 DEG C After drying, the level hole carbon negative pole material with multi-element doping is obtained, that is, obtains described lithium ion carbon negative pole material.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108993382A (en) * 2018-06-25 2018-12-14 湖南烯富环保科技有限公司 A kind of defluorination material and its regeneration method based on bacteria residue
CN109626370A (en) * 2019-01-21 2019-04-16 青岛科技大学 The preparation and its application of biomass-based porous carbon materials based on sycamore seed
CN109879266A (en) * 2019-03-05 2019-06-14 中南大学 A kind of preparation method of porous C-base composte material
CN111003710A (en) * 2020-01-17 2020-04-14 宿州学院 Method for preparing nitrogen-doped graded porous carbon by using waste medicine residues and application of method

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102502630A (en) * 2011-11-30 2012-06-20 河北科技大学 Method for preparing activated carbon from penicillin or terramycin strain residues
CN103964412A (en) * 2013-01-30 2014-08-06 北京化工大学 Preparation method of nitrogen-doped porous-structure carbon material
CN105316069A (en) * 2015-11-06 2016-02-10 江西康丰生物科技有限公司 Technology for refining biochar through waste fungus residue recovery
WO2016143439A1 (en) * 2015-03-06 2016-09-15 国立大学法人大阪大学 Porous body including bacterial cellulose and polymer, and method of manufacturing same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102502630A (en) * 2011-11-30 2012-06-20 河北科技大学 Method for preparing activated carbon from penicillin or terramycin strain residues
CN103964412A (en) * 2013-01-30 2014-08-06 北京化工大学 Preparation method of nitrogen-doped porous-structure carbon material
WO2016143439A1 (en) * 2015-03-06 2016-09-15 国立大学法人大阪大学 Porous body including bacterial cellulose and polymer, and method of manufacturing same
CN105316069A (en) * 2015-11-06 2016-02-10 江西康丰生物科技有限公司 Technology for refining biochar through waste fungus residue recovery

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108993382A (en) * 2018-06-25 2018-12-14 湖南烯富环保科技有限公司 A kind of defluorination material and its regeneration method based on bacteria residue
CN108993382B (en) * 2018-06-25 2021-09-07 湖南烯富环保科技有限公司 Defluorination material based on mushroom dregs and regeneration method thereof
CN109626370A (en) * 2019-01-21 2019-04-16 青岛科技大学 The preparation and its application of biomass-based porous carbon materials based on sycamore seed
CN109879266A (en) * 2019-03-05 2019-06-14 中南大学 A kind of preparation method of porous C-base composte material
CN111003710A (en) * 2020-01-17 2020-04-14 宿州学院 Method for preparing nitrogen-doped graded porous carbon by using waste medicine residues and application of method

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