CN110526350A - A kind of CDI multi-stage porous activated carbon electrodes and its preparation method and application using HAP cracking self-activation - Google Patents
A kind of CDI multi-stage porous activated carbon electrodes and its preparation method and application using HAP cracking self-activation Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
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- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
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Abstract
The invention belongs to saline solns desalting technology fields, specially a kind of method for preparing CDI electrode active material using hydroxyapatite (HAP) cracking self-activation, it is characterized in that, carbon source comprising HAP is heat-treated at a temperature of being greater than or equal to 1000 DEG C, self-activation is carried out while cracking HAP and to carbonized product, obtains the CDI electrode material.The present invention innovatively utilizes HAP in the at a temperature of self-cleavage and synchronous release vapor and CO more than or equal to 1000 DEG C2One step building multilevel hole material is come to the mechanism of carbonization carbon surface self-activation.In addition, it has also been found that there is unexpected electro adsorption capacity in salting liquid CDI adsorbing domain using the HAP material that cleavage method obtains at said temperatures.
Description
Technical field
The invention belongs to electrochemical capacitor deionization fields, and in particular to a kind of preparation of electrode active material.
Background technique
Since population increases, industrial development and climate change, shortage of fresh water have become a global menace
Problem.In order to solve this problem, extensive concern has been caused using seawater and bitter production fresh water.Capacitive deionization
(CDI) due to low energy consumption, low cost, energy conservation and environmental protection, be easy to the characteristics of regenerating is widely used in salt ion in recent years
Removing.
The desalting performance of capacitive deionization is heavily dependent on the structure and property of electrode material.Commercial activated carbons by
It is commonly used as CDI electrode in the advantage with high specific surface area and low cost, however, commercial activated carbons are mainly by micropore
Composition, shows not being inconsistent, therefore lead to low hole utilization efficiency between big specific surface area and actually available surface area, limits
The diffusion and migration of salt ion are made.Wang etc. (J.Mater.Chem.A, 2016,4,10858-10868) uses traditional micro-
Electrode of the mesoporous activated carbon as CDI, the salt adsorption capacity measured is only 5.12mg/g, and its average adsorption rate is relatively low.
So far, various carbon-based materials have been applied to CDI, such as carbon nanotube, carbon aerogels, mesoporous carbon, carbon fiber
Peacekeeping graphene.However, for the carbon-based material of CDI being synthesized by the chemical substance of petroleum derivation above, having can not
Reproducibility unquestionably also will increase the cost of preparation and be difficult to prepare and apply on a large scale.Work with hierarchical porous structure
Property charcoal the characteristics of high electric conductivity and good electro adsorption capacity and is widely studied, due to low with preparation cost currently, more
The synthesis of grade pore structure active carbon is broadly divided into following two method: one is by additional template method, i.e., by carbon matrix precursor with
Additional hard template is sufficiently mixed, and after high temperature cabonization, it is more to prepare to carry out dissolution to additional template by strong acid
The active carbon of grade pore structure.Patrick Strubel etc. (Adv.Funct.Mater, 2015,25,287-297) is received using ZnO
Rice grain is adequately mixed as additional template with sucrose, by being carbonized at high temperature, passes through handling for strong acid later
To HPCs.Another method is graded porous carbon derived from biomass own cells characteristic, i.e., by the way that biomass and chemistry is living
Agent is mixed, high temperature cabonization, to obtain porous mesoporous activated carbon.Yu etc. (ACS Sustainable Chem.Eng,
2018,6,15325-15332) first bagasse is put into autoclave and carries out hydro-thermal process, then by the product after hydro-thermal
It is carbonized in tube furnace with KOH, is finally handled with concentrated hydrochloric acid after evenly mixing, obtain multistage mesoporous activated carbon after dry.However, with
Need to add additional template in the upper method for synthesizing multistage mesoporous activated carbon, unquestionably this by increase material preparation at
This, it is difficult to extensive synthesis, and also preparation process is complicated, and the use of chemical activating agent pollutes, and the use of strong acid causes to set
The problems such as standby corrosion.
Summary of the invention
It there are preparation process complexity, the additional addition template of needs and is made for existing CDI electrode active material preparation method
Material the technical deficiencies such as capacitive adsorption performance is undesirable, split it is an object of the present invention to provide a kind of using HAP
A kind of method that solution self-activation prepares CDI electrode active material, it is intended to have in CDI absorption using completely new mechanism preparation excellent
The electrode material of anisotropic energy.
Second purpose of the invention is, provides a kind of added with the HAP cracking self-activation preparation CDI electrode activity material
The CDI electrode of material.
Third purpose of the present invention is, provides the preparation method of the CDI electrode and in salting liquid capacitive desalination
Application.It is intended to improve the removal of salt ion in salting liquid, the flowing of NaCl solution in the electrodes is promoted, so as to improve absorption
Capacity.
It is a primary object of the present invention to solve the CDI absorption problem of salting liquid, for this purpose, the present invention provides a kind of utilizations
The method that hydroxyapatite (HAP) cracking self-activation prepares CDI electrode active material, the carbon source comprising HAP is being greater than or is being waited
It is heat-treated at a temperature of 1000 DEG C, cracks HAP and to carbonized product self-activation, obtain the CDI electrode material.
Main innovation of the present invention is: (1) innovatively using hydroxyapatite at a temperature of being greater than or equal to 1000 DEG C
Self-cleavage and synchronous release vapor, CO2、H2One step building multi-stage porous material is come to the mechanism that carbonization carbon surface is produced from activation
Material.(2) present invention innovatively has found, is adsorbed and is led in salting liquid CDI using the HAP material that cleavage method obtains at said temperatures
Domain has unexpected absorption property.Relative to existing preparation thinking, the present invention provides one kind without passing through acid etching etc.
Method stripper plate carries out the completely new preparation mechanism of pore-creating, i.e., is innovatively being greater than or equal to 1000 DEG C of temperature using hydroxyapatite
Under autothermic cracking characteristic and pyrolysis product primary activation mechanism.Moreover, present invention research has surprisingly been found that, passes through hydroxyl
Material made from base apatite autothermic cracking activation method has excellent absorption property in CDI absorption.
Preferably, the carbon source comprising HAP is the carbon source comprising HAP.The carbon source can be nitrogen-free carbon source
Or nitrogenous carbon source.The nitrogen-free carbon source is, for example, sucrose, macromolecule organic etc..The nitrogenous carbon source is preferably albumen
Matter, lipid etc..
Further preferably, the carbon source comprising HAP is the nitrogenous carbon source comprising HAP.
Preferably, the carbon source comprising HAP is animal bone.The animal bone is, for example, ox bone, pig bone
Deng.
Animal bone is washed with water in advance, is dried, is ground, screens particle at 200 mesh.
In the present invention, the heat treatment temperature needs to control so guarantee that HAP's is abundant at 1000 DEG C or more
Cracking and to the self-activation of carbon, to unexpectedly significantly improve the adsorption capacity of CDI.
Preferably, the temperature of heat treatment is 1000~1200 DEG C.
Preferably, the atmosphere of heat treatment process is protective atmosphere；For example, nitrogen atmosphere, argon atmosphere.
Preferably, heating rate is 5~15 DEG C/min.
Preferably, heat treatment time is 1~3h.
Preparation method of the present invention, HAP decomposes removing by cracking, without removing pore-creating by acid elution.
Preparation method of the present invention can be ultrasonically treated the product of heat treatment.For example, by the heat of acquisition
Reason product is ultrasonically treated in deionized water solution.Ultrasonic time is, for example, 5-15 hours；Preferably 5~10h.
CDI electrode active material produced by the present invention, specific surface area 884.63-2147.43m2/ g, nitrogen content are
1.38-5.03%, oxygen content 2.54-10.56%.
The present invention also provides a kind of CDI electrodes, including collector, and are compounded in the electrode material of collection liquid surface
Layer；The active material includes conductive agent, binder and the CDI electrode active material.
Preferably, the collector is carbon paper, graphite paper, carbon cloth or titanium plate, preferably titanium plate is as collector.
Preferably, the conductive agent is at least one of acetylene black, conductive black.
Preferably, the binder is at least one of PVDF, PTFE.
Preferably, the content of conductive agent is 1~10wt.% in electrode material layer；The content of binder be 1~
10wt.%.
The present invention also provides the preparation method of the CDI electrode described in one kind, by the conductive agent, binder and
CDI electrode active material obtains slurry with solvent pulp, is subsequently coated at the surface of collector, is drying to obtain.
The electrode gross mass applied on a current collector is about each electrode 45-49mg.
Such as: by the active material of 80wt%, the acetylene black of 10wt% and the PVDF of 10wt% are dissolved in as adhesive
In the NMP of 2mL, then it is ultrasonically treated and stirs 30 minutes to form uniform slurry.1mL mixed slurry is coated in collector
On, and be dried overnight at 120 DEG C, to completely remove NMP.The electrode gross mass applied on a current collector is about each electrode
45mg。
The present invention also provides the application of the CDI electrode described in one kind, the capacitive deionization for salting liquid is handled.
Compared with prior art, the excellent effect of the present invention is that:
1, the present invention is innovatively using hydroxyapatite in the at a temperature of self-cleavage and synchronization more than or equal to 1000 DEG C
Discharge vapor, CO2, step building multilevel hole material is come to the mechanism that carbonization carbon surface is produced from activation；It is of the present invention
Hydroxyapatite sufficiently cracks under the described conditions, without using Template removal to be removed again.
2, the present invention innovatively has found, is inhaled using the HAP material that cleavage method obtains at said temperatures in salting liquid CDI
Attached field has unexpected absorption property.
The study found that the CDI electrode is in 1Ag-1Current density under have 110.5F g-1Specific capacitance, 100
The capacitor retention rate that 98.7% is illustrated in secondary continuous charge and discharge cycles test, when as CDI electrode, in original solution
500mg L-1NaCl solution in, under the voltage of 1.2V, it is shown that 19.35mg g-1Electro Sorb capacity.
Detailed description of the invention
Fig. 1 is the nitrogen adsorption desorption isotherm of BC-HPCs-1000 prepared by embodiment 1, graph of pore diameter distribution；In figure, BC
Refer to bone before handling, BC-HPCs-1000 refers to embodiment 1 treated product.
Fig. 2 is the XRD diffraction pattern and infrared spectrogram of the material of the preparation of embodiment 1 front and back；In figure, BC refers to processing prebone
Head, BC-HPCs-950 head of phalanx be heat-treated at 950 DEG C after product, refer to embodiment 1 treated product.
Fig. 3 is the release variation with temperature curve of gas in bone cracking process；
Fig. 4 is the x-ray photoelectron spectroscopy figure of BC-HPCs-1000 prepared by embodiment 1；
Fig. 5 is the cyclic voltammetry curve of BC-HPCs-1000 electro-chemical test prepared by embodiment 1, and constant current charge-discharge is bent
Line and uninterrupted charge-discharge test figure；
In above-mentioned each figure, BC indicates original bone；BC-HPCs-700 represents bone and is carbonized to 700 DEG C；BC-HPCs-
800, which represent bone, is carbonized to 800 DEG C；BC-HPCs-900 represents bone and is carbonized to 900 DEG C；BC-HPCs-1000 represents bone
Head is carbonized to 1000 DEG C, and AC represents commercial activated carbons (green source activity charcoal Co., Ltd, Pingdingshan City, the 200 mesh powder of purchase
Last wood activated charcoal, specific surface area 1109.03m2/g)。
Specific embodiment
With reference to embodiment, the present invention is further described in detail, thus make the purpose of the present invention,
Technical solution and advantage are more clear.It should be appreciated that description presented herein is merely for the sake of the preferred reality for illustrating purpose
Example explains the present invention, and but not to limit the present invention, in actual application, those skilled in the art is according to this hair
The bright modifications and adaptations made, still fall within protection scope of the present invention.
Following experimental methods as described in the examples are unless otherwise specified conventional method；The reagent and material
Material, unless otherwise specified, commercially obtains.
Embodiment 1
By the Os Bovis seu Bubali (BC) of purchase with 100 DEG C of deionized water wash 2 hours with remove some remaining protein and
Fat, it is 24 hours dry in 80 DEG C of vacuum drying oven, then by the animal bone grind into powder after drying, pass through standard screen
By dry bone screening at the particle of 200 mesh, the bone powder after then taking 5g to screen is placed in a quartz tube furnace
1000 DEG C are heated to the rate of heat addition of 5 DEG C/min in nitrogen atmosphere, is kept at this temperature 3h, later by system natural cooling
To room temperature.Obtained black powder sample is placed in ultrasound 15h in ultrasonic instrument, it is dry with distilled water flushing, and at 60 DEG C
12 hours.Thus obtained sample is BC-HPCs-1000.The specific surface area of BC-HPCs-1000 is 2147.43m2/ g, nitrogen quantity
It is 3.52%, oxygen content 6.35%.
Embodiment 2
The pretreatment of bone uses the preparation process of embodiment 1, and the bone powder after then taking 5g to screen is placed in one
1000 DEG C are heated to the rate of heat addition of 5 DEG C/min in nitrogen atmosphere in quartz tube furnace, is kept at this temperature 2h, later will
System cooled to room temperature.Obtained black powder sample is placed in ultrasound 15h in ultrasonic instrument, with distilled water flushing, and
It is 12 hours dry at 60 DEG C.Thus obtained sample is BC-HPCs-1000-2.The specific surface area of BC-HPCs-1000-2 is
2016.37m2/ g, nitrogen content 3.14%, oxygen content 6.27%.
Embodiment 3
The pretreatment of bone uses the preparation process of embodiment 1, and the bone powder after then taking 5g to screen is placed in one
1000 DEG C are heated to the rate of heat addition of 5 DEG C/min in nitrogen atmosphere in quartz tube furnace, is kept at this temperature 2h, later will
System cooled to room temperature.Obtained black powder sample is placed in ultrasound 10h in ultrasonic instrument, with distilled water flushing, and
It is 12 hours dry at 60 DEG C.Thus obtained sample is BC-HPCs-1000-3.The specific surface area of BC-HPCs-1000-3 is
1770.57m2/ g, nitrogen content 1.38%, oxygen content 2.54%.
Embodiment 4
The pretreatment of bone uses the preparation process of embodiment 1, and the bone powder after then taking 5g to screen is placed in one
1200 DEG C are heated to the rate of heat addition of 5 DEG C/min in nitrogen atmosphere in quartz tube furnace, is kept at this temperature 3h, later will
System cooled to room temperature.Obtained black powder sample is placed in ultrasound 15h in ultrasonic instrument, with distilled water flushing, and
It is 12 hours dry at 60 DEG C.Thus obtained sample is BC-HPCs-1200.The specific surface area of BC-HPCs-1200 is
1935.12m2/ g, nitrogen content 0.07%, oxygen content 0.13%.
Comparative example 1
It is compared with embodiment 1, difference is only that, the temperature for changing heat treatment is 700 DEG C, specific as follows: the pre- place of bone
Reason uses the preparation process of embodiment 1, and the bone powder after then taking 5g to screen is placed in a quartz tube furnace in nitrogen
Atmosphere is heated to 700 DEG C with the rate of heat addition of 5 DEG C/min, is kept at this temperature 2h, later by system cooled to room temperature.
Obtained black powder sample is placed in ultrasound 10h in ultrasonic instrument, it is 12 hours dry with distilled water flushing, and at 60 DEG C.
Thus obtained sample is BC-HPCs-700.The specific surface area of BC-HPCs-700 is 884.63m2/ g, nitrogen content 5.03%,
Oxygen content is 10.56%.
Comparative example 2
It is compared with embodiment 1, difference is only that, the temperature for changing heat treatment is 800 DEG C, specific as follows: the pre- place of bone
Reason uses the preparation process of embodiment 1, and the bone powder after then taking 5g to screen is placed in a quartz tube furnace in nitrogen
Atmosphere is heated to 800 DEG C with the rate of heat addition of 5 DEG C/min, is kept at this temperature 2h, later by system cooled to room temperature.
Obtained black powder sample is placed in ultrasound 10h in ultrasonic instrument, it is 12 hours dry with distilled water flushing, and at 60 DEG C.
Thus obtained sample is BC-HPCs-800.The specific surface area of BC-HPCs-800 is 931.46m2/ g, nitrogen content 4.86%,
Oxygen content is 10.16%.
Comparative example 3
It is compared with embodiment 1, difference is only that, the temperature for changing heat treatment is 900 DEG C, specific as follows: the pre- place of bone
Reason uses the preparation process of embodiment 1, and the bone powder after then taking 5g to screen is placed in a quartz tube furnace in nitrogen
Atmosphere is heated to 900 DEG C with the rate of heat addition of 5 DEG C/min, is kept at this temperature 2h, later by system cooled to room temperature.
Obtained black powder sample is placed in ultrasound 10h in ultrasonic instrument, it is 12 hours dry with distilled water flushing, and at 60 DEG C.
Thus obtained sample is BC-HPCs-900.The specific surface area of BC-HPCs-900 is 1123.12m2/ g, nitrogen content are
4.06%, oxygen content 8.01%.
Comparative example 4
It is compared with embodiment 1, difference is only that, the temperature for changing heat treatment is 950 DEG C, and does not have to ultrasonic treatment, specifically
As follows: the pretreatment of bone uses the preparation process of embodiment 1, and the bone powder after then taking 5g to screen is placed in a quartz
950 DEG C are heated to the rate of heat addition of 5 DEG C/min in nitrogen atmosphere in tube furnace, is kept at this temperature 2h, later by system
Cooled to room temperature.Obtained black powder sample is rinsed by deionized water, and 12 hours dry at 60 DEG C.Thus
The sample arrived is BC-HPCs-950.The specific surface area of BC-HPCs-950 is 1311.53m2/g, and nitrogen content 3.26%, oxygen contains
Amount is 7.54%.And passing through the XRD diffraction graph discovery of Fig. 2 a, the peak of hydroxyapatite still remains, therefore in 950 DEG C of hydroxyl phosphorus
Lime stone does not crack.
Comparative example 5
Mechanism is not cracked using HAP of the invention, HAP mechanism is taken off using carbonization+pickling,
It is compared with embodiment 1, difference is only that, the temperature for changing heat treatment is 800 DEG C, is handled finally by acid, specifically
As follows: the pretreatment of bone uses the preparation process of embodiment 1, and the bone powder after then taking 5g to screen is placed in a quartz
800 DEG C are heated to the rate of heat addition of 5 DEG C/min in nitrogen atmosphere in tube furnace, is kept at this temperature 2h, later by system
Cooled to room temperature.By obtained black powder sample by the nitric acid treatment 5h of obtained black powder sample 2mol/L,
It is 12 hours dry with distilled water flushing to neutrality, and at 60 DEG C.Thus obtained sample is BC-HPCs-800-2.BC-
The specific surface area of HPCs-800-2 is 1453.32m2/g, nitrogen content 3.96%, oxygen content 10.01%.Obviously, pass through acid
The more untreated height of specific surface area after processing shows at this time by the undecomposed hydroxyapatite of acid dissolution, to be formed big
The pore structure of amount leads to the raising of specific surface area.
Fig. 1 is nitrogen adsorption desorption and the pore size distribution curve of the classifying porous carbon material of preparation, compared with BC, BC-
HPCs-1000 shows the nitrogen adsorption desorption of IV type, has quick nitrogen adsorption under relatively low pressure, shows that there are micro-
There is apparent hysteresis loop under high relative pressure in hole, shows that there is mesoporous and macropores.
Fig. 2 be processing before, the XRD and infrared figure of the product that are handled at a temperature of different disposal.
Fig. 2 a is the XRD diffraction pattern of the porous activated carbon of preparation, when bone (BC) is not pyrolyzed, and at 950 DEG C
At a temperature of, show the diffraction maximum of hydroxyapatite, and after 1000 DEG C of pyrolysis, the diffraction maximum of hydroxyapatite disappears,
And there is distinctive 002 diffraction maximum of carbon material, illustrate that bone is converted to carbon, hydroxyapatite is decomposed.Fig. 2 b
Further illustrate this as a result, there are still carbonate group and phosphate radical, display hydroxyls at 950 DEG C to bone for its infrared spectrogram
The presence of base apatite, but when 1000 DEG C of temperature, carbonate group and phosphate groups completely disappear after carbonization, illustrate hydroxyl
Apatite is decomposed.
In order to prove the presence of self-activation, Fig. 3 shows mass spectrogram of the bone in carbonisation, when carburizing temperature is
At 900 DEG C, H2Rise with the curve of CO, shows that carbonisation releases hydrogen and carbon monoxide, when temperature is increased to 1000 DEG C
When CO2Curve decline, shows that carbon dioxide is consumed, reacts with carbonized carbonaceous, produce self-activation, has occurred following anti-
It answers:
C+H2O→CO+H2 (1)
C+CO2→2CO (2)
Application examples 1
Electro-chemical test is carried out to porous active Carbon Materials are prepared in above-described embodiment 3.Specific operation process are as follows: by 8mg
The BC-HPCs-1000-3 porous activated carbon of nitrogen oxygen original position codope for preparing of embodiment 3,1mg conductive black and 1mg PVDF
It is dissolved in 1mLNMP as adhesive mixing, is then ultrasonically treated and stirs 30 minutes, form uniform slurries, then take 100 μ
L mixed slurry is coated in 1 × 1cm2Graphite paper, it is dried overnight at 120 DEG C.Prepared electrode is placed in the NaCl electricity of 1mol/L
It solves in liquid, is to electrode with platinum electrode, silver/silver chlorate carries out electrochemistry survey as reference electrode, using three electrode test methods
Examination.
Its cyclic voltammetry curve (figure under 5-200mV/s sweep speed is surveyed according to the porous carbon materials that embodiment 3 obtains
5a), CV curve of the electrode under different sweep speeds remains similar rectangular shape, even if in the scanning of 200mV/s
The shape that class rectangle is still maintained under rate illustrates that the material has excellent rate capacities.Fig. 5 b is BC-HPCs-1000-
Constant current charge-discharge curve of 3 electrodes under 0.2-10A/g charging and discharging currents density further confirms that the material has good speed
Rate capacity.When current density further proves that it has compared with the height of same type of material for 0.2A/g, specific capacitance 110.5F/g
Good chemical property.This may be since the material has high specific surface area, porosity abundant.And work as the material
After circulation 100 times, still there is 98.7% capacitor retention rate (Fig. 4 c).
Application examples 2
Under the similarity condition of application examples 1 under 1A/g current density, respectively to comparative example 1, comparative example 2,3 He of comparative example
Porous carbon materials contrast test constant current charge-discharge test, obtained specific capacitance prepared by embodiment 1 is respectively 50.04,60.4,
90.7 and 110.5F/g, it is thus found that BC-HPCs-1000 has optimal chemical property.
Application examples 3
To above-mentioned comparative example 1, comparative example 2 is prepared porous carbon materials in comparative example 3 and embodiment 3 and is mentioned by above-mentioned
The preparation method of the capacitive deionization electrode of confession: by the active material of 80wt%, the acetylene black of 10wt% and the PVDF of 10wt%
It is dissolved in the NMP of 2mL, is then ultrasonically treated and stirs 30 minutes to form uniform slurry.1mL mixed slurry is coated in
On collector, and it is dried overnight at 120 DEG C.By obtained CDI electrode assembling at CDI unit, apply one between positive and negative anodes
Salting liquid to be processed is delivered in CDI unit by fixed applied voltage by peristaltic pump, carries out capacitive deionization test.Such as
Shown in Fig. 5 a, under the application voltage of 1.2V, BC-HPCs-700, BC-HPCs-800 are measured in the NaCl solution of 500mg/L,
The Electro Sorb capacity of BC-HPCs-900, BC-HPCs-1000-3 and AC are distinguished, 6.89,9.42,12.11,19.35 and 5.36mg/
g.It is compared with AC, the porous carbon of preparation has a high salt adsorption capacity and the high salt rate of adsorption.
Application examples 4
Pass through the preparation side of the capacitive deionization electrode of above-mentioned offer to porous carbon materials are prepared in above-described embodiment 3
Method: by the BC-HPCs-1000 of 80wt%, the acetylene black of 10wt% and the PVDF of 10wt% are dissolved in the NMP of 2mL, are then surpassed
Sonication simultaneously stirs 30 minutes to form uniform slurry.On a current collector by the coating of 1mL mixed slurry, and at 120 DEG C it does
A dry night.By obtained CDI electrode assembling at CDI unit, applies certain applied voltage between positive and negative anodes, pass through peristaltic pump
Salting liquid to be processed is delivered in CDI unit, capacitive deionization test is carried out.Controlling the voltage in CDI device is 0.8V,
The flow rate of NaCl salting liquid is 15mL/min, and the initial concentration of NaCl is 500mg/L.
Application examples 5
The porous carbon materials that the nitrogen oxygen being prepared in above-described embodiment 3 is adulterated in situ by above-mentioned offer capacitor go from
The preparation method of sub-electrode: by the BC-HPCs-1000 of 80wt%, the acetylene black of 10wt% and the PVDF of 10wt% are dissolved in 2mL
NMP in, be then ultrasonically treated and stir 30 minutes to form uniform slurry.On a current collector by the coating of 1mL mixed slurry,
And it is dried overnight at 120 DEG C.By obtained CDI electrode assembling at CDI unit, apply certain outer power-up between positive and negative anodes
Salting liquid to be processed, is delivered in CDI unit by pressure by peristaltic pump, carries out capacitive deionization test.It controls in CDI device
Voltage be 1.0V, the flow rate of NaCl salting liquid is 15mL/min, and the initial concentration of NaCl is 500mg/L.
Application examples 6
The porous carbon materials that the nitrogen oxygen being prepared in above-described embodiment 3 is adulterated in situ by above-mentioned offer capacitor go from
The preparation method of sub-electrode: by the BC-HPCs-1000-3 of 80wt%, the acetylene black of 10wt% and the PVDF of 10wt% are dissolved in
In the NMP of 2mL, then it is ultrasonically treated and stirs 30 minutes to form uniform slurry.1mL mixed slurry is coated in collector
On, and it is dried overnight at 120 DEG C.By obtained CDI electrode assembling at CDI unit, apply between positive and negative anodes certain outer
Salting liquid to be processed is delivered in CDI unit by making alive by peristaltic pump, carries out capacitive deionization test.Control CDI dress
Voltage in setting is 1.2V, and the flow rate of NaCl salting liquid is 15mL/min, and the initial concentration of NaCl is 500mg/L.
Application examples 7
The porous carbon materials that the nitrogen oxygen being prepared in above-described embodiment 1 is adulterated in situ by above-mentioned offer capacitor go from
The preparation method of sub-electrode: by the BC-HPCs-1000 of 80wt%, the acetylene black of 10wt% and the PVDF of 10wt% are dissolved in 2mL
NMP in, be then ultrasonically treated and stir 30 minutes to form uniform slurry.On a current collector by the coating of 1mL mixed slurry,
And it is dried overnight at 120 DEG C.By obtained CDI electrode assembling at CDI unit, apply certain outer power-up between positive and negative anodes
Salting liquid to be processed, is delivered in CDI unit by pressure by peristaltic pump, carries out capacitive deionization test.It controls in CDI device
Voltage be 1.2V, the flow rate of NaCl salting liquid is 15mL/min, and the initial concentration of NaCl is 250mg/L.
Application examples 8
The porous carbon materials that the nitrogen oxygen being prepared in above-described embodiment 1 is adulterated in situ by above-mentioned offer capacitor go from
The preparation method of sub-electrode: by the BC-HPCs-1000 of 80wt%, the acetylene black of 10wt% and the PVDF of 10wt% are dissolved in 2mL
NMP in, be then ultrasonically treated and stir 30 minutes to form uniform slurry.On a current collector by the coating of 1mL mixed slurry,
And it is dried overnight at 120 DEG C.By obtained CDI electrode assembling at CDI unit, apply certain outer power-up between positive and negative anodes
Salting liquid to be processed, is delivered in CDI unit by pressure by peristaltic pump, carries out capacitive deionization test.It controls in CDI device
Voltage be 1.2V, the flow rate of NaCl salting liquid is 15mL/min, and the initial concentration of NaCl is 1000mg/L.
Application examples 9
The porous carbon materials adulterated in situ to the nitrogen oxygen being prepared in above-described embodiment 1 are gone by the capacitor of above-mentioned offer
The preparation method of ion electrode: by the BC-HPCs-1000 of 80wt%, the acetylene black of 10wt% and the PVDF of 10wt% are dissolved in
In the NMP of 2mL, then it is ultrasonically treated and stirs 30 minutes to form uniform slurry.1mL mixed slurry is coated in collector
On, and it is dried overnight at 120 DEG C.By obtained CDI electrode assembling at CDI unit, apply between positive and negative anodes certain outer
Salting liquid to be processed is delivered in CDI unit by making alive by peristaltic pump, carries out capacitive deionization test.Control CDI dress
Voltage in setting is 1.2V, and the flow rate of NaCl salting liquid is 15mL/min, and the initial concentration of NaCl is 1500mg/L.
Using application examples 1 similar to test condition, the Electro Sorb capacity of each embodiment and comparative example is measured, is tested
Condition and it the results are shown in Table 1.
Table 1
In summary, preparation method of the present invention can use the obtained one kind of HAP cracking and have in terms of CDI absorption
There is the material of excellent adsorption effect.
Claims (10)
1. a kind of method for preparing CDI electrode active material using HAP cracking self-activation, which is characterized in that by the carbon comprising HAP
Source more than or equal to 1000 DEG C at a temperature of be heat-treated, crack HAP and to carbonized product self-activation, obtain the CDI
Electrode material.
2. the method for preparing CDI electrode active material using HAP cracking self-activation as described in claim 1, which is characterized in that
The carbon source comprising HAP is the carbon source comprising HAP, preferably comprising the nitrogenous carbon source of HAP.
3. the method for preparing CDI electrode active material using HAP cracking self-activation as described in claim 1, which is characterized in that
The carbon source comprising HAP is animal bone.
4. the method for preparing CDI electrode active material using HAP cracking self-activation as claimed in claim 3, which is characterized in that
Animal bone is washed with water in advance, is dried, is ground, screens particle at 200 mesh.
5. the method for preparing CDI electrode active material using HAP cracking self-activation as claimed in claim 3, which is characterized in that
The atmosphere of heat treatment process is protective atmosphere；Heating rate is 5~15 DEG C/min；Time is 1~3h.
6. the method for preparing CDI electrode active material using HAP cracking self-activation as described in claim 1, which is characterized in that
The heat-treated products of acquisition are ultrasonically treated in deionized water solution.
7. a kind of CDI electrode, which is characterized in that including collector, and be compounded in the electrode material layer of collection liquid surface；It is described
Active material include CDI electrode activity material made from any one of conductive agent, binder and claim 1~6 preparation method
Material.
8. CDI electrode as claimed in claim 7, which is characterized in that the collector is carbon paper, graphite paper, carbon cloth or titanium
Plate；
The conductive agent is at least one of acetylene black, conductive black；
The binder is at least one of PVDF, PTFE；
In electrode material layer, the content of conductive agent is 1~10wt.%；The content of binder is 1~10wt.%.
9. the preparation method of CDI electrode described in a kind of claim 7 or 8, which is characterized in that by the conductive agent, bonding
Agent and CDI electrode active material obtain slurry with solvent pulp, are subsequently coated at the surface of collector, are drying to obtain.
10. the application of CDI electrode described in a kind of claim 7 or 8, which is characterized in that the capacitive deionization for salting liquid
Processing.
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