CN109037680A - A kind of porous Carbon anode energy storage material of the N doping of long circulating performance and preparation method thereof - Google Patents
A kind of porous Carbon anode energy storage material of the N doping of long circulating performance and preparation method thereof Download PDFInfo
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- CN109037680A CN109037680A CN201810865212.4A CN201810865212A CN109037680A CN 109037680 A CN109037680 A CN 109037680A CN 201810865212 A CN201810865212 A CN 201810865212A CN 109037680 A CN109037680 A CN 109037680A
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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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- 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 discloses the porous Carbon anode energy storage material and preparation method of a kind of derivative N doping of waste, i.e. first by the diaper centralized recovery after baby's use, the superabsorbent particle water for taking out the yellowish-brown of the inside is simultaneously freeze-dried for -50 DEG C of temperature control, the dry presoma of yellowish-brown is obtained in nitrogen, under conditions of helium or argon gas protection, control heating rate is warming up to 400-1000 DEG C for 1-10 DEG C/min and carries out calcining 15-300min, then cooled to room temperature, calcining crude product is obtained to be ground under conditions of ambient humidity is within 40% with agate mortar, pickling, then again with secondary distilled water centrifuge washing 3 times of 60 DEG C, last 80 DEG C of temperature control is dried in vacuo, up to the porous Carbon anode energy storage material of the N doping of long circulating performance.It is with high initial capacity and excellent cyclical stability and good high rate performance.Preparation method is simple, low in cost, is suitable for large-scale production.
Description
Technical field
The present invention relates to a kind of battery electrode materials, and in particular to a kind of porous Carbon anode of the N doping of long circulating performance
Energy storage material and preparation method belong to materialogy field.
Background technique
Since graphite is as cell negative electrode material, under the conditions of storing up lithium, only limited capacity, therefore it is based on hard carbon mechanism
The more capacity of porous Carbon stock.And when sodium electricity cathode, the chaotic configuration of playing cards room model is more conducive to storing
Sodium ion, therefore be the storage for being advantageous to lithium ion and sodium ion for the composite material of porous hard carbon matrix.But
These lack the doping vario-property of heteroatom from pyrolytic carbon, because the modification of heteroatom can be improved not high electricity itself
Electron conductivity, while the doping of heteroatom can effectively improve the active site of electrode material itself.In conclusion electric at present
There are capacity to be limited for pond negative electrode material, recycles the technical problems such as unstable.
Not being taken seriously after baby's diaper application at present, while ununified processing, in conclusion by me
Recycling applied on energy-storage battery electrode have good prospect, can either completely for its waste recovery benefit
With conducive to environmental protection；Preferable cycle characteristics is shown in energy storage negative electrode material simultaneously, and compared to graphite electrode
(372mAh/g) shows specific capacity with higher.It is about 515mAh/g as 300 circle number capacity of lithium electricity circulation.In addition,
When as anode material of lithium-ion battery, 1000 circle capacity of circulation is about 199mAh/g.Prepared electrode material clearly has
There are good specific capacity and considerable circulating ring number.
And superabsorbent particle water (Super Absorbent Particle, SAP) is a kind of new function macromolecule water uptake
Material.It has the function of the several hundred high water absorptions to thousands of times of water of absorptance itself weight, and water retention property is excellent, once water suction is swollen
When being expanded into as hydrogel, water is difficult to separate pressurization.Therefore, it is in personal hygiene article, industrial and agricultural production, soil
The every field such as Wood construction have extensive use.Superabsorbent particle water is a kind of macromolecular containing hydrophilic radical and cross-linked structure,
It is made again through being saponified by Fanta etc. using starch-grafted polyacrylonitrile earliest.It is divided by raw material, there is starch-series (graft, carboxylic first
Base etc.), cellulose-based (carboxy methylation, graft etc.), synthetic polymer system (polyacrylic, polyethenol series etc.) it is several big
Class.Wherein polyacrylic high hydroscopic resin compared with starch-series and it is cellulose-based compare, have that production cost is low, simple process, life
The series of advantages such as high-efficient, water absorbing capacity is strong, shelf life of products is long are produced, the research hotspot in the current field is become.In a system
The carbon structure of multilayer can be formed after the technology preparation of column.A series of this target material by modifications can become a kind of excellent
The cell negative electrode material of matter.
The water-absorbing resins of high energy also have the characteristics of own: 1. super absorbent resin is a kind of with macromolecule solid network
The functional polymer of binding structure；2. hydrophilic radical (hydroxyl and carboxyl etc.) content is more, hydrophily is strong, good water-retaining property；3. being formed
Reticular structure；4. by a large amount of hydrophilic radicals on hydrogen bond and molecular resin chain aquation occurs for hydrone, hydrophilic radical from
Solution；5. the anion for ionizing generation is fixed on macromolecular chain, the repulsive interaction between anion makes high score subnet Shu Zhankai, shape
At hole；6. free cation concentration in resin network, which increases, generates osmotic pressure inside and outside network, three-dimensional crosslinking structure expansion
The corresponding elastic shrinkage generated is finally reached water suction balance.Meanwhile calcined product (the derivative carbon material of class graphene) conduct
The negative electrode material of secondary cell possesses higher specific capacity, better cycle performance.Introducing miscellaneous element in material itself simultaneously will
Stablizing for specific capacity can more be facilitated to be promoted, it will increase the application prospect of material itself.
Summary of the invention
The purpose of the present invention is to solve above-mentioned cell negative electrode materials under charge and discharge cycles capacity attenuation comparatively fast with
And the more low technical problem of specific capacity and a kind of porous Carbon anode energy storage material of the N doping that provides long circulating performance, the length
The porous Carbon anode energy storage material of the N doping of cycle performance, due to high N doping content and has more active site
Deng, therefore have under charge and discharge cycles, the slow advantage of capacity attenuation.
The second object of the present invention is to provide a kind of porous Carbon anode energy storage material of the N doping of above-mentioned long circulating performance
The preparation method of material, the preparation method have production cost low, useless due to using discarded baby's diaper as raw material
The characteristics of object recycles.And waste reclamation is always the hot issue of social concerns, for discarding returning for diaper
It is to kill two birds with one stone that receipts, which are used,.
Technical principle of the invention
The present invention is contained by the hydroscopic high-molecular resin Sodium Polyacrylate absorption in the diaper after discarded baby's use
The waste (excretas, sundries such as urine of baby's excretion) of nitrogen, then obtains xerogel presoma by freeze-drying,
Target product most is prepared through high-temperature calcination activation pickling afterwards.
Water-absorbing resin as a kind of new function macromolecule, gather around by application of the calcined material in lithium ion, sodium-ion battery
Have the advantages of following energy storage material: 1. only lithium ion, the storage of sodium ion and electronics, transmission do not mention three-dimensional porous structure
Effective space and path are supplied；2. the contact area with electrolyte can be increased, the active material on electrode is made full use of, is allowed
Lithium, sodium enter sufficiently into the inside of material in charge and discharge process；3. electrode material charge and discharge process can also be effectively inhibited
In capacity attenuation, prevent from reuniting；4. finally reducing electrode material polarization and the internal resistance of cell, the circulation for greatly improving material being steady
Qualitative and high rate performance.
The reaction process of experiment is (principle of granular precursor formation hydrogel) substantially as described below: super absorbent resin is
A kind of functional polymer with macromolecule solid network binding structure；Superabsorbent particle water of the water-absorbing resin from baby's diaper；
1. hydrophilic radical content is more, hydrophily is strong, good water-retaining property；Using the super water sorption to resin, by acquirement
Superabsorbent particle water carries out absorbing deionized water or metal salt solution (such as nickel nitrate aqueous solution)；
2. forming reticular structure；There is (free state) in the form of an ion in deionized water in nickel nitrate crystal；
3. by a large amount of hydrophilic radicals on hydrogen bond and molecular resin chain aquation occurs for hydrone, hydrophilic radical from
Solution；
4. the anion for ionizing generation is fixed on macromolecular chain, the repulsive interaction between anion makes high score subnet beam exhibition
It opens, forms hole；
5. free cation concentration in resin network, which increases, generates osmotic pressure inside and outside network, three-dimensional crosslinking structure expansion
The corresponding elastic shrinkage generated is finally reached water suction balance (forming hydrogel)；
6. when the miscellaneous Element Solution in solution is completely into water-absorbing resin skeletal internal (in infants miscellaneous Element Solution
Keep 37 DEG C or so and baby during shaking table shake back and forth), finally by being freeze-dried collected hydrogel
It is dried to dry gel (being yellowish-brown coloured particles by the transform hydrogel of yellowish-brown).
Technical solution of the present invention
A kind of porous Carbon anode energy storage material of the N doping of long circulating performance, is mainly made of tri- kinds of elements of N, C, O,
It is prepared by a method comprising the following steps:
(1) recovery processing of diaper is discarded
By the diaper centralized recovery after baby's use, the protective layer of diaper outer layer is separated, takes out the yellowish-brown of the inside
The superabsorbent particle water (NSAP) of color, and without containing other such as cottons of the sundries from diaper etc.；
The superabsorbent particle water of yellowish-brown is that the urine for absorbing baby due to the superabsorbent particle water (SAP) in diaper forms
, the superabsorbent particle water is Sodium Polyacrylate, includes inorganic salts, urea, urea and a variety of nitrogens in the urine of baby
Amino acid；
(2) preparation of dry presoma
The yellowish-brown superabsorbent particle water that step (1) obtains is put into freeze drier cold controlled at -50 DEG C of progress
It is lyophilized dry, disappears to obtain the dry presoma (NSAP-W) of yellowish-brown to moisture；
(3) the dry granular precursor of the resulting yellowish-brown of step (2) is transferred in tube furnace, 25 DEG C of initial temperature,
Under conditions of the protection of nitrogen, helium or argon gas, control heating rate is that 1-10 DEG C/min is warming up to 400-1000 DEG C and carries out the
Primary calcining 15-300min, preferably control heating rate are that 3 DEG C/min is warming up to 650-750 DEG C of progress calcining 60- for the first time
180min, then cooled to room temperature, obtains calcining crude product；
(4) by the resulting calcining crude product of step (3) ambient humidity be 40% under conditions of agate mortar into
Row grinding 30min, then carry out pickling, again with secondary distilled water centrifuge washing 3 times of 60 DEG C after pickling, finally controlled at
80 DEG C of progress vacuum drying treatment 12h obtain the porous Carbon anode energy storage material (NSAPC-W) of the N doping of long circulating performance；
The pickling uses concentration for the hydrochloric acid of 0.0001mol/L-10mol/L, sulfuric acid or aqueous solution of nitric acid
Being stirred control revolving speed after 30min is 3000-12000r/min centrifuge washing 10-15min, it is preferred to use concentration is
Control revolving speed is 8000r/min centrifuge washing 15min, centrifugation gained after the aqueous hydrochloric acid solution of 0.1mol/L is stirred 30min
Precipitating first use distilled water centrifuge washing 3 times, then use dehydrated alcohol centrifuge washing 3 times again, complete acid cleaning process.
A kind of porous Carbon anode energy storage material of the N doping of above-mentioned long circulating performance due to high storage lithium and
Sodium capacity is stored up, therefore can be used as the negative electrode material of lithium ion and sodium-ion battery, applied to lithium ion and sodium-ion battery
In cathode preparation, to be applied in lithium ion battery or sodium-ion battery.
Advantageous effects of the invention
The porous Carbon anode energy storage material of the N doping of a kind of long circulating performance of the invention, due to using absorbing
The superabsorbent particle water of the urine of baby, which will be containing a large amount of miscellaneous element, especially
It is nitrogen, is three-dimensional network frame structure by drying, high-temperature calcination, grinding, pickling, drying using it, finally obtains length
The porous Carbon anode energy storage material of the N doping of cycle performance.
Further, the porous Carbon anode energy storage material of the N doping of a kind of long circulating performance of the invention, due to quoting water
Gel is constructed, and wherein water-absorption particle is as a kind of new functional macromolecule material, can lock more hydrones and water-soluble
Liquid.And hydrogel internal crosslinking braiding structure is formed, before being freeze-dried containing miscellaneous element water-absorption particle into solid particle
Body design construction three-dimensional porous structure.The three-dimensional box of Nitrogen element is constructed by this three-dimensional cross-linked reticular structure
Frame so that the porous Carbon anode energy storage material of N doping under the porous framework of itself have more good cycle performance and
High rate performance.
Further, the porous Carbon anode energy storage material of the N doping of a kind of long circulating performance of the invention, by function high score
Son and Nitrogen element impurity phase combine, and obtain the porous Carbon anode energy storage of N doping by freeze-drying, high-temperature calcination, high-temperature activation
Material significantly improves cyclical stability of the carbon-based material in charge and discharge process, is scrap concrete as really commercial
Stable carbon-based material pushed ahead a step, have significant practical application.
Further, the porous Carbon anode energy storage material of the N doping of a kind of long circulating performance of the invention, due to high score
Sub- thermal decomposition product Sodium Polyacrylate is substrate framework material, and shape characteristic is in uniform regular distribution, provides the length of material charge and discharge
Circulation；The nitrogen of impurity from infant urine is uniform and is embedded in porous carbon substrate lamella in stable, guarantees
The height ratio capacity of the porous Carbon anode energy storage material of the N doping of final resulting long circulating performance.
Further, the porous Carbon anode energy storage material of the N doping of a kind of long circulating performance of the invention, due to preparing
Using superabsorbent particle water used in discarded baby's diaper in journey, therefore preparation cost is cheap, turns waste into wealth.
Further, the preparation method letter of the porous Carbon anode energy storage material of the N doping of a kind of long circulating performance of the invention
It is single, it is low in cost, it is suitable for large-scale production.
Detailed description of the invention
Fig. 1: the porous Carbon anode energy storage material of the N doping of 1 gained long circulating performance of embodiment is saturating under 1 μm of multiplying power
Penetrate electron microscope；
Fig. 2: the X-ray diffraction spectrogram (XRD) of the dry presoma of the resulting yellowish-brown of 1 step of embodiment (2)；
Fig. 3: the porous Carbon anode energy storage material of the N doping of 1 gained long circulating performance of embodiment is prepared into lithium ion battery
Cathode after the cycle performance figure of the button-shaped lithium ion battery that assembles in the case where current density is i=2000mA/g, in figure
Abscissa is circulating ring number, and ordinate is the capacity reached；
Fig. 4: the porous Carbon anode energy storage material of the N doping of 1 gained long circulating performance of embodiment is prepared into sodium-ion battery
Cathode after the cycle performance figure of the button-shaped sodium battery that assembles in the case where current density is i=2000mA/g；It is horizontal in figure
Coordinate is circulating ring number, and ordinate is the capacity reached.
Specific embodiment
The present invention is further described below by embodiment and in conjunction with attached drawing, but is not intended to limit the present invention.
The electrochemistry of the porous Carbon anode energy storage material of the N doping of long circulating performance obtained in the embodiment of the present invention
It can be tested by electrochemical workstation and blue electrical measurement test system；Electrochemical workstation used is occasion China electrochemical operation
It stands；Blue electrical measurement test system uses LAND-CT2001.Electrochemical property test is tested using 2032/2016 type button cell, knob
Button battery full of argon gas glove box in assemble, in glove box the content value of water and the content value of oxygen be held at 0.1ppm with
Under.
Transmission electron microscope used is produced using JEM company, the saturating transmission electron microscope of model 2100F.
X-ray diffractometer used, Bruker company production model are D8advance.
Thermogravimetric instrument used is NETZSCH STA 409PC.
Embodiment 1
A kind of porous Carbon anode energy storage material of the N doping of long circulating performance, is mainly made of tri- kinds of elements of N, C, O,
It is prepared by a method comprising the following steps:
(1) recovery processing of diaper is discarded
By the diaper centralized recovery after baby's use, the protective layer of diaper outer layer is separated, takes out the yellowish-brown of the inside
The superabsorbent particle water of color；The superabsorbent particle water of yellowish-brown is the Sodium Polyacrylate after absorbing infant urine；
(2) preparation of dry presoma
The superabsorbent particle water for the yellowish-brown that step (1) obtains is put into freeze drier and is carried out controlled at -50 DEG C
It is dry, it disappears to obtain the dry presoma (NSAP-W) of yellowish-brown to moisture；
(3) the dry granular precursor of the resulting yellowish-brown of step (2) is transferred in tube furnace, 25 DEG C of initial temperature,
Under conditions of nitrogen protection, control heating rate is warming up to 650 DEG C for 3 DEG C/min and carries out calcining 180min, then naturally cold
But to room temperature, calcining crude product is obtained；
(4) by the resulting calcining crude product of step (3) ambient humidity be 40% under conditions of agate mortar into
Row grinding 30min, then carry out pickling, again with secondary distilled water centrifuge washing 3 times of 60 DEG C after pickling, finally controlled at
80 DEG C of progress vacuum drying treatment 12h obtain the porous Carbon anode energy storage material (NSAPC-W) of the N doping of long circulating performance；
The pickling, that is, revolving speed is controlled after using concentration to be stirred 30min for the aqueous hydrochloric acid solution of 0.1mol/L is
8000r/min centrifuge washing 15min is centrifuged resulting precipitating and first uses distilled water centrifuge washing 3 times, then uses dehydrated alcohol again
Centrifuge washing 3 times, complete acid cleaning process.
Using transmission electron microscope to the porous Carbon anode energy storage material of the N doping of above-mentioned resulting long circulating performance at 1 μm
Under transmission electron microscope picture as shown in Figure 1, as can be seen from Figure 1 the N doping of resulting long circulating performance porous Carbon anode storage
Energy material has the graded porous structure of three-dimensional framework, has been indicated above the transmission for being suitable for lithium ion or sodium ion；
The dry presoma (NSAP-W) of the resulting yellowish-brown of above-mentioned steps (2) is surveyed using X-ray diffractometer
Calmly, resulting X-ray diffraction spectrogram is as shown in Fig. 2, the presoma that as can be seen from Figure 2 above-mentioned resulting yellowish-brown is dried
It (NSAP-W) is a kind of non-crystalline material, without apparent diffraction maximum, being indicated above carbonized product is a kind of amorphous material.
It calculates in mass ratio, the porous Carbon anode energy storage material of the N doping of long circulating performance: the conductive agent (conduction
Agent is acetylene black): bonding agent (binder is Kynoar PVDF) is the ratio of 8:1:1, by above-mentioned long circulating
The slurry that the porous Carbon anode energy storage material of N doping and conductive agent, bonding agent of energy are obtained after mixing, then will slurry
Material be coated in copper foil current collector, obtain lithium ion battery cathode be assembled into glove box as half-cell button-shaped lithium from
Sub- battery.Assembled button battery is finally subjected to electro-chemical test in blue electrical measurement test system and electrochemical workstation,
Current density be the cycle performance of i=2000mA/g as shown in Figure 3, as can be seen from Figure 3 obvious stable electrochemistry
Can, electrode material has been indicated above with preferable cycle performance.
It calculates in mass ratio, with organic solvent, (described has the porous Carbon anode energy storage material of the N doping of long circulating performance
Solvent is: N methyl pyrrolidone NMP) it is used as solvent；According to conductive agent (conductive agent is acetylene black): bonding agent (institute
The binder stated is Kynoar PVDF): for the ratio of 8:1:1, by the porous Carbon anode of N doping of above-mentioned long circulating performance
Slurry, is then coated in copper foil current collector by the slurry that energy storage material and conductive agent, bonding agent are obtained after mixing,
The cathode for obtaining sodium-ion battery is assembled into button-shaped sodium-ion battery as half-cell in glove box.It finally will be assembled
Button battery carries out electro-chemical test in blue electrical measurement test system and electrochemical workstation, is i=2000mA/g in current density
Cycle performance as shown in Figure 4, as can be seen from Figure 4 obvious stable chemical property, has been indicated above electrode material
With preferable cycle performance.
Embodiment 2
A kind of porous Carbon anode energy storage material of the N doping of long circulating performance, is mainly made of tri- kinds of elements of N, C, O,
It is prepared by a method comprising the following steps:
(1) recovery processing of diaper is discarded
By the diaper centralized recovery after baby's use, the protective layer of diaper outer layer is separated, takes out the yellowish-brown of the inside
The superabsorbent particle water of color；The superabsorbent particle water of yellowish-brown is the Sodium Polyacrylate after absorbing infant urine；
(2) preparation of dry presoma
The superabsorbent particle water for the yellowish-brown that step (1) obtains is put into freeze drier and is carried out controlled at -50 DEG C
It is dry, it disappears to obtain the dry presoma (NSAP-W) of yellowish-brown to moisture；
(3) the dry granular precursor of the resulting yellowish-brown of step (2) is transferred in tube furnace, 25 DEG C of initial temperature,
Under conditions of argon gas protection, control heating rate is warming up to 650 DEG C for 3 DEG C/min and carries out calcining 180min, then naturally cold
But to room temperature, calcining crude product is obtained；
(4) by the resulting calcining crude product of step (3) ambient humidity be 40% under conditions of agate mortar into
Row grinding 30min, then carry out pickling, again with secondary distilled water centrifuge washing 1 time of 60 DEG C after pickling, finally controlled at
80 DEG C of progress vacuum drying treatment 12h, obtain the porous Carbon anode energy storage material of the N doping of long circulating performance；
The pickling, that is, revolving speed is controlled after using concentration to be stirred 30min for the aqueous hydrochloric acid solution of 0.1mol/L is
8000r/min centrifuge washing 15min, be centrifuged it is resulting precipitating first use distilled water centrifuge washing 3 times, then again with dehydrated alcohol from
The heart washs 3 times, completes acid cleaning process.
Embodiment 3
A kind of porous Carbon anode energy storage material of the N doping of long circulating performance, is mainly made of tri- kinds of elements of N, C, O,
It is prepared by a method comprising the following steps:
(1) recovery processing of diaper is discarded
By the diaper centralized recovery after baby's use, the protective layer of diaper outer layer is separated, takes out the yellowish-brown of the inside
The superabsorbent particle water of color；The superabsorbent particle water of yellowish-brown is the Sodium Polyacrylate after absorbing infant urine；
(2) preparation of dry presoma
The superabsorbent particle water for the yellowish-brown that step (1) obtains is put into freeze drier and is carried out controlled at -50 DEG C
It is dry, it disappears to obtain the dry presoma (NSAP-W) of yellowish-brown to moisture；
(3) the dry granular precursor of the resulting yellowish-brown of step (2) is transferred in tube furnace, 25 DEG C of initial temperature,
Under conditions of argon gas protection, control heating rate is warming up to 750 DEG C for 5 DEG C/min and carries out calcining 180min, then naturally cold
But to room temperature, calcining crude product is obtained；
(4) by the resulting calcining crude product of step (3) ambient humidity be 40% under conditions of agate mortar into
Row grinding 30min, then carry out pickling, again with secondary distilled water centrifuge washing 3 times of 60 DEG C after pickling, finally controlled at
80 DEG C of progress vacuum drying treatment 12h, obtain the porous Carbon anode energy storage material of the N doping of long circulating performance；
The pickling, that is, revolving speed is controlled after using concentration to be stirred 30min for the aqueous hydrochloric acid solution of 0.1mol/L is
8000r/min centrifuge washing 15min, be centrifuged it is resulting precipitating first use distilled water centrifuge washing 3 times, then again with dehydrated alcohol from
The heart washs 3 times, completes acid cleaning process.
Embodiment 4
A kind of porous Carbon anode energy storage material of the N doping of long circulating performance, is mainly made of tri- kinds of elements of N, C, O,
It is prepared by a method comprising the following steps:
(1) recovery processing of diaper is discarded
By the diaper centralized recovery after baby's use, the protective layer of diaper outer layer is separated, takes out the yellowish-brown of the inside
The superabsorbent particle water of color；The superabsorbent particle water of yellowish-brown is the Sodium Polyacrylate after absorbing infant urine；
(2) preparation of dry presoma
The superabsorbent particle water for the yellowish-brown that step (1) obtains is put into freeze drier and is carried out controlled at -50 DEG C
It is dry, it disappears to obtain the dry presoma (NSAP-W) of yellowish-brown to moisture；
(3) the dry granular precursor of the resulting yellowish-brown of step (2) is transferred in tube furnace, 25 DEG C of initial temperature,
Under conditions of argon gas protection, control heating rate is warming up to 850 DEG C for 10 DEG C/min and carries out calcining 180min, then naturally cold
But to room temperature, calcining crude product is obtained；
(4) by the resulting calcining crude product of step (3) ambient humidity be 40% under conditions of agate mortar into
Row grinding 30min, then carry out pickling, again with secondary distilled water centrifuge washing 3 times of 60 DEG C after pickling, finally controlled at
80 DEG C of progress vacuum drying treatment 12h, obtain the porous Carbon anode energy storage material of the N doping of long circulating performance；
The pickling, that is, revolving speed is controlled after using concentration to be stirred 30min for the aqueous hydrochloric acid solution of 0.1mol/L is
8000r/min centrifuge washing 15min, be centrifuged it is resulting precipitating first use distilled water centrifuge washing 3 times, then again with dehydrated alcohol from
The heart washs 3 times, completes acid cleaning process.
Embodiment 5
A kind of porous Carbon anode energy storage material of the N doping of long circulating performance, is mainly made of tri- kinds of elements of N, C, O,
It is prepared by a method comprising the following steps:
(1) recovery processing of diaper is discarded
By the diaper centralized recovery after baby's use, the protective layer of diaper outer layer is separated, takes out the yellowish-brown of the inside
The superabsorbent particle water of color；The superabsorbent particle water of yellowish-brown is the Sodium Polyacrylate after absorbing infant urine；
(2) preparation of dry presoma
The superabsorbent particle water for the yellowish-brown that step (1) obtains is put into freeze drier and is carried out controlled at -50 DEG C
It is dry, it disappears to obtain the dry presoma (NSAP-W) of yellowish-brown to moisture；
(3) the dry granular precursor of the resulting yellowish-brown of step (2) is transferred in tube furnace, 25 DEG C of initial temperature,
Under conditions of nitrogen protection, control heating rate is warming up to 750 DEG C for 5 DEG C/min and carries out calcining 180min, then naturally cold
But to room temperature, calcining crude product is obtained；
(4) by the resulting calcining crude product of step (3) ambient humidity be 40% under conditions of agate mortar into
Row grinding 30min, then carry out pickling, again with secondary distilled water centrifuge washing 3 times of 60 DEG C after pickling, finally controlled at
80 DEG C of progress vacuum drying treatment 12h, obtain the porous Carbon anode energy storage material of the N doping of long circulating performance；
The pickling, that is, revolving speed is controlled after using concentration to be stirred 30min for the aqueous hydrochloric acid solution of 0.1mol/L is
8000r/min centrifuge washing 15min, be centrifuged it is resulting precipitating first use distilled water centrifuge washing 3 times, then again with dehydrated alcohol from
The heart washs 3 times, completes acid cleaning process.
Embodiment 6
A kind of porous Carbon anode energy storage material of the N doping of long circulating performance, is mainly made of tri- kinds of elements of N, C, O,
It is prepared by a method comprising the following steps:
(1) recovery processing of diaper is discarded
By the diaper centralized recovery after baby's use, the protective layer of diaper outer layer is separated, takes out the yellowish-brown of the inside
The superabsorbent particle water of color；The superabsorbent particle water of yellowish-brown is the Sodium Polyacrylate after absorbing infant urine；
(2) preparation of dry presoma
The superabsorbent particle water for the yellowish-brown that step (1) obtains is put into freeze drier and is carried out controlled at -50 DEG C
It is dry, it disappears to obtain the dry presoma (NSAP-W) of yellowish-brown to moisture；
(3) the dry granular precursor of the resulting yellowish-brown of step (2) is transferred in tube furnace, 25 DEG C of initial temperature,
Under conditions of nitrogen protection, control heating rate is warming up to 750 DEG C for 5 DEG C/min and carries out calcining 60min, then natural cooling
To room temperature, calcining crude product is obtained；
(4) by the resulting calcining crude product of step (3) ambient humidity be 40% under conditions of agate mortar into
Row grinding 30min, then carry out pickling, again with secondary distilled water centrifuge washing 3 times of 60 DEG C after pickling, finally controlled at
80 DEG C of progress vacuum drying treatment 12h, obtain the porous Carbon anode energy storage material of the N doping of long circulating performance；
The pickling, that is, revolving speed is controlled after using concentration to be stirred 30min for the aqueous hydrochloric acid solution of 0.1mol/L is
8000r/min centrifuge washing 15min, be centrifuged it is resulting precipitating first with distilled water from
The heart washs 3 times, then uses dehydrated alcohol centrifuge washing 3 times again, completes acid cleaning process.
Embodiment 7
A kind of porous Carbon anode energy storage material of the N doping of long circulating performance, is mainly made of tri- kinds of elements of N, C, O,
It is prepared by a method comprising the following steps:
(1) recovery processing of diaper is discarded
By the diaper centralized recovery after baby's use, the protective layer of diaper outer layer is separated, takes out the yellowish-brown of the inside
The superabsorbent particle water of color；The superabsorbent particle water of yellowish-brown is the Sodium Polyacrylate after absorbing infant urine；
(2) preparation of dry presoma
The superabsorbent particle water for the yellowish-brown that step (1) obtains is put into freeze drier and is carried out controlled at -50 DEG C
It is dry, it disappears to obtain the dry presoma (NSAP-W) of yellowish-brown to moisture；
(3) the dry granular precursor of the resulting yellowish-brown of step (2) is transferred in tube furnace, 25 DEG C of initial temperature,
Under conditions of nitrogen protection, control heating rate is warming up to 750 DEG C for 3 DEG C/min and carries out calcining 60min, then natural cooling
To room temperature, calcining crude product is obtained；
(4) by the resulting calcining crude product of step (3) ambient humidity be 40% under conditions of agate mortar into
Row grinding 30min, then carry out pickling, again with secondary distilled water centrifuge washing 3 times of 60 DEG C after pickling, finally controlled at
80 DEG C of progress vacuum drying treatment 12h, obtain the porous Carbon anode energy storage material of the N doping of long circulating performance；
The pickling, that is, revolving speed is controlled after using concentration to be stirred 30min for the aqueous hydrochloric acid solution of 0.1mol/L is
8000r/min centrifuge washing 15min, be centrifuged it is resulting precipitating first use distilled water centrifuge washing 3 times, then again with dehydrated alcohol from
The heart washs 3 times, completes acid cleaning process.
Embodiment 8
A kind of porous Carbon anode energy storage material of the N doping of long circulating performance, is mainly made of tri- kinds of elements of N, C, O,
It is prepared by a method comprising the following steps:
(1) recovery processing of diaper is discarded
By the diaper centralized recovery after baby's use, the protective layer of diaper outer layer is separated, takes out the yellowish-brown of the inside
The superabsorbent particle water of color；The superabsorbent particle water of yellowish-brown is the Sodium Polyacrylate after absorbing infant urine；
(2) preparation of dry presoma
The superabsorbent particle water for the yellowish-brown that step (1) obtains is put into freeze drier and is carried out controlled at -50 DEG C
It is dry, it disappears to obtain the dry presoma (NSAP-W) of yellowish-brown to moisture；
(3) the dry granular precursor of the resulting yellowish-brown of step (2) is transferred in tube furnace, 25 DEG C of initial temperature,
Under conditions of nitrogen protection, control heating rate is warming up to 650 DEG C for 3 DEG C/min and carries out calcining 60min, then natural cooling
To room temperature, calcining crude product is obtained；
(4) by the resulting calcining crude product of step (3) ambient humidity be 40% under conditions of agate mortar into
Row grinding 30min, then carry out pickling, again with secondary distilled water centrifuge washing 3 times of 60 DEG C after pickling, finally controlled at
80 DEG C of progress vacuum drying treatment 12h, obtain the porous Carbon anode energy storage material of the N doping of long circulating performance；
The pickling, that is, revolving speed is controlled after using concentration to be stirred 30min for the aqueous hydrochloric acid solution of 0.1mol/L is
8000r/min centrifuge washing 15min, be centrifuged it is resulting precipitating first use distilled water centrifuge washing 3 times, then again with dehydrated alcohol from
The heart washs 3 times, completes acid cleaning process.
In conclusion a kind of preparation method of the porous Carbon anode energy storage material of the derivative N doping of waste of the invention,
Porous carbon materials have been obtained from simple preparation method, have shown fabulous electrochemistry cycle performance, excellent chemical property
It is attributed to three-dimensional frame structure derived from the superabsorbent particle water inside its discarded diaper and many work of nitrogen bring
Property site.
It is described the prefered embodiments of the present invention in detail above in conjunction with attached drawing, still, the present invention is not limited to above-mentioned realities
The detail in mode is applied, within the scope of the technical concept of the present invention, a variety of letters can be carried out to technical solution of the present invention
Monotropic type, these simple variants all belong to the scope of protection of the present invention.
Claims (5)
1. a kind of preparation method of the porous Carbon anode energy storage material of the N doping of long circulating performance, it is characterised in that specifically include
Following steps:
(1) recovery processing of diaper is discarded
By the diaper centralized recovery after baby's use, the protective layer of diaper outer layer is separated, takes out the yellowish-brown of the inside
Superabsorbent particle water, and do not contain other sundries from diaper；
The superabsorbent particle water of the yellowish-brown be the urine of baby is absorbed due to the superabsorbent particle water in baby's diaper and
At, the superabsorbent particle water is Sodium Polyacrylate；
(2) preparation of dry presoma
The yellowish-brown superabsorbent particle water that step (1) obtains is put into freeze drier freeze controlled at -50 DEG C and is done
It is dry, it disappears to obtain the dry presoma of yellowish-brown to moisture；
(3) the dry granular precursor of the resulting yellowish-brown of step (2) is transferred in tube furnace, 25 DEG C of initial temperature, in nitrogen
Under conditions of gas, helium or argon gas protection, control heating rate is that 1-10 DEG C/min is warming up to 400-1000 DEG C of progress for the first time
15-300min is calcined, then cooled to room temperature, obtains calcining crude product；
(4) the resulting calcining crude product of step (3) is ground under conditions of ambient humidity is within 40% with agate mortar
Then 30min carries out pickling, again with secondary distilled water centrifuge washing 3 times of 60 DEG C after pickling, finally controlled at 80 DEG C into
Row vacuum drying treatment 12h obtains the porous Carbon anode energy storage material of the N doping of long circulating performance；
The pickling, that is, use concentration for hydrochloric acid, sulfuric acid or the aqueous solution of nitric acid of 0.0001 mol/L-10 mol/L into
Controlling revolving speed after row stirring 30min is 3000-12000 r/min centrifuge washing 10-15min, is centrifuged resulting precipitating first with steaming
It distilled water centrifuge washing 3 times, then uses dehydrated alcohol centrifuge washing 3 times again, completes acid cleaning process.
2. a kind of preparation method of the porous Carbon anode energy storage material of the N doping of long circulating performance as described in claim 1,
It is characterized in that control heating rate is that 3 DEG C/min is warming up to 650-750 DEG C of progress calcining 60- for the first time in step (3)
180min。
3. a kind of preparation method of the porous Carbon anode energy storage material of the N doping of long circulating performance as claimed in claim 2,
It is characterized in that after pickling described in step (4) uses concentration to be stirred 30min for the aqueous hydrochloric acid solution of 0.1 mol/L
Control revolving speed is 8000r/min centrifuge washing 15min, is centrifuged resulting precipitating and first uses distilled water centrifuge washing 3 times, then uses again
Dehydrated alcohol centrifuge washing 3 times, complete acid cleaning process.
4. a kind of porous Carbon anode of the N doping for long circulating performance that preparation method as claimed in claim 1,2 or 3 obtains
Energy storage material.
5. a kind of porous Carbon anode energy storage material of the N doping of long circulating performance as claimed in claim 4 can be used as lithium ion
With the negative electrode material of sodium-ion battery, applied in lithium ion battery or sodium-ion battery.
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