CN105543925B - A kind of electrolyte based on Carbonaceous mesophase and its method for preparing carbon film - Google Patents
A kind of electrolyte based on Carbonaceous mesophase and its method for preparing carbon film Download PDFInfo
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Abstract
The invention belongs to field of electroplating, and in particular to a kind of electrolyte and its preparation and application.Electrolyte, containing biomass derived Carbonaceous mesophase and organic solvent, in organic solvent described in every 1000 mL, containing 0.01 g ~ 10 g the biomass derived Carbonaceous mesophase.The electrolyte of the present invention has the characteristics of environmental protection, electrical conductivity is high, and electroplating operations can be carried out under lower temperature and voltage using the electrolyte of the present invention（30 ~ 70 DEG C ,≤30 V）, there is low, safe, the easy-operating advantage of energy consumption.
Description
Technical field
The invention belongs to field of electroplating, and in particular to a kind of electrolyte and its preparation and application.
Background technology
Carbon film is a kind of hydrogen-containing carbon film with amorphous state and micro- crystalline structure, and with its carbon atom track sp2And sp3's
Ratio difference can be divided into diamond-like carbon film (with sp3Based on, Diamond-like Carbon, DLC) and amorphous carbon coating
(with sp2Based on, Graphite-like Carbon, GLC).Because carbon film has a series of excellent physical and chemical performances, such as
High rigidity, low-friction coefficient, highly thermally conductive property, high resistivity, good wear-resistant and corrosion resistance and from infrared to ultraviolet
Highly transmissive ratio in relative broad range etc., thus it is widely used in the fields such as machinery, electronics, chemistry, military affairs and Aero-Space.This
Outside, graphene film is due to anti-microbial property, being more applied to biomedical material surface modification.
In recent years, substantial amounts of research has been done for the preparation, modification and application of carbon film, scholar both domestic and external.With regard to preparation side
For method, typically using the synthetic method based on gas phase such as physical vapour deposition (PVD) and chemical vapour deposition technique, such as magnetron sputtering, from
Beamlet deposition, pulsed laser deposition and plasma enhanced chemical vapor deposition etc., can typically be obtained using these methods
The carbon film of high quality, deposition velocity are also very fast.But the base reservoir temperature that vapor phase method requirement is higher, large area film forming are more difficult；
Meanwhile deposited under gas phase condition, it is necessary to equipment it is more complicated, energy consumption is big, and price is high, and which has limited the development of carbon film
Using.To overcome the shortcomings of above-mentioned gas phase high energy synthetic method, domestic and foreign scholars have carried out liquid electrodeposition method and have prepared carbon film
Research.Compared with vapour deposition, liquid electrodeposition has advantages below：1) reaction can be carried out at normal temperatures and pressures, and be not at
Poised state, mutually there is favourable condition to the new metastable state of formation；2) reaction is carried out in the liquid phase, and it is anti-to be easily controlled electrode
The condition answered, it is reproducible, it is easier to obtain the film of uniform quality；3) suitable industrialized production, in flat surface and do not advise
Then surface can large area film forming；4) depositing device is simple, saves the energy and raw material, low in the pollution of the environment, is easier to reach industrialization
The scale of production and requirement.
Literature search to prior art is found, when preparing carbon film using Content by Electrodeposition in Liquid Phase, electrolyte (i.e. carbon
Source) organic solution is generally, active methyl CH is included in its molecule3Or CHn (4-n)+, and be directly bonded with polar group, Er Qieqi
Dielectric constant is high, viscosity is small.Conventional carbon source has：Acetonitrile, N,N-dimethylformamide, methanol, ethanol etc. therein one
Kind is several.Problem present in selected carbon source and operating process is when electrochemical deposition method prepares carbon film at present：1) some carbon
Source such as acetonitrile is noxious material, pollutes environment；2) electrolytic conductivity is low, and will not typically be dissociated into ion, and degree of polarization is weak；
3) several kilovolts of high voltages (1000-3000V) need to be applied or deposited using extremely low temperature (subzero 30 DEG C) decreased voltage (2~5V),
Not only high energy consumption, the feature of environmental protection is poor, and danger coefficient is high, is unfavorable for operating, the shortcomings that can not realizing large-scale industrial application.
The content of the invention
In view of the above the shortcomings that prior art, it is an object of the invention to provide one kind to be based on biomass derived carbonaceous
The electrolyte and its prepare the electro-plating method of carbon film that interphase is prepared, with overcome in electrolyte in the prior art carbon source not environmentally,
Electrolytic conductivity is low, electro-deposition when high energy consumption, danger coefficient is high, the problem of being not easy to realize scale application.
To achieve these goals and other related purposes, the present invention adopt the following technical scheme that：
The first aspect of the present invention, there is provided a kind of electrolyte, containing biomass derived Carbonaceous mesophase and organic solvent,
In organic solvent described in per 1000mL, the biomass derived Carbonaceous mesophase containing 0.01g~10g.
It is further preferred that the biomass derived carbonaceous mesophase containing 0.01g~5g in organic solvent described in per 1000mL
Phase.
Preferably, the organic solvent is selected from acetamide, methanol, ethanol, acetic acid, ethylene glycol, DMF
(DMF) any one or more combination in.
Preferably, conducting salt is also contained in the electrolyte.
It is further preferred that the conducting salt be selected from sodium chloride, potassium chloride, magnesium chloride, calcium chloride, potassium acetate, magnesium acetate,
Any in KI, sodium iodide, sodium bromide, sodium acetate, potassium nitrate, sodium nitrate, magnesium nitrate, potassium sulfate, sodium sulphate, magnesium sulfate
Kind or a variety of combinations.
It is further preferred that in organic solvent described in per 1000mL, the conducting salt containing 0.1g~50g.It is it is highly preferred that every
In organic solvent described in 1000mL, the conducting salt containing 0.2g~50g.
Preferably, additive is also contained in the electrolyte.
It is further preferred that the additive is selected from the nanometer of metal salt, metallo-organic compound or nonmetalloid
Any of grain or a variety of combinations.
It is further preferred that the additive selected from silica, ferric acetyl acetonade, cupric perchlorate, nickel acetylacetonate, in
Any one or more combinations.
In the preferred embodiments of the present invention, the silica uses nano silicon.That is, the silica
Particle size range is 1nm~100nm.
It is further preferred that in organic solvent described in per 1000mL, the additive containing 0.1g~10g.
The second aspect of the present invention, there is provided the preparation method of aforementioned electrolyte, comprise the following steps：
When in the electrolyte, when not containing conducting salt and additive, it is only necessary to including step：
(1) biomass derived carbonaceous mesophase is added in organic solvent by proportioning, dissolves, it is organic molten to obtain interphase
Liquid.
Preferably, when in the electrolyte, when also containing conducting salt but not containing additive, methods described, including step
Suddenly on the basis of (1), in addition to step：
(2) conducting salt is added in gained interphase organic solution into step (1) by proportioning, dissolves, obtain mixed liquor, i.e.,
Can.
Preferably, when in the electrolyte, also containing conducting salt and during additive, methods described is in step step (1)
On the basis of, in addition to step：
(2) additive is added in gained interphase organic solution into step (1) by proportioning, dissolves, obtain mixed liquor；Then
Conducting salt is added into gained mixed liquor by proportioning, dissolves, produces electrolyte.
It is further preferred that in step (1), during dissolving, stirring is until form black even liquid.
It is further preferred that in step (2), additive is added while stirring.
It is further preferred that in step (2), dissolved by heating, the temperature control of heating is at 30~70 DEG C.
It is stirred it is further preferred that in step (2), while heating until forming liquid bottom without solid content.
The third aspect of the present invention, there is provided purposes of the aforementioned electrolyte in field of electroplating prepares carbon film.
The fourth aspect of the present invention, it is further provided a kind of electro-plating method, comprise the following steps：
(1) treatment before plating：Matrix material is handled according to the preprocess method in conventional plating process；
(2) pretreated matrix material is put into aforementioned electrolyte and electroplated；
(3) sample is taken out, drying is rinsed, produces carbon film.
Preferably, methods described also includes step (4), and carbon film obtained by step (3) is heat-treated, and cools down.
Carbon film requires under different use environments to carbon film structure, if necessary to amorphous carbon-film, then does not just have at heat
Reason, method during plating, only includes step (1)~(3).If necessary to the high carbon film of crystallinity, for example diamond lattic structure
, then in plating, it is also necessary to carry out step (4) heat treatment.
Preferably, in step (1), matrix material may be selected from conventional any matrix material that can be used for being electroplated,
Such as electro-conductive glass, silicon chip, titanium, copper, magnesium, stainless steel etc..
Preferably, in step (2), electroplated by the way of direct current electrode position or pulse plating.
Preferably, in step (2), the operation temperature of plating is 30~70 DEG C, and electroplating time is 5~120min, and electric current is close
Spend for 0.1~5A/dm2, voltage is 1~30V.
Preferably, in step (3), using deionized water rinsing.
Preferably, carbon film heat treatment temperature is 500~1000 DEG C in step (4), and heat-treating atmosphere is that nitrogen, argon gas etc. are lazy
Property gas.
The fifth aspect of the present invention, there is provided a kind of carbon film, prepared by foregoing electro-plating method.
Compared with prior art, the beneficial effects of the present invention are：
(1) electrolyte of the invention has the characteristics of environmental protection, electrical conductivity is high, can be compared with low temperature using the electrolyte of the present invention
Electroplating operations (30~70 DEG C ,≤30V) are carried out under degree and voltage, there is low, safe, the easy-operating advantage of energy consumption.
(2) the carbon film uniform quality for preparing, carbon film structure controllability are good when being electroplated using the electrolyte of the present invention.
Brief description of the drawings
Fig. 1：For the SEM photograph of the carbon film prepared in the embodiment of the present invention 1.
Fig. 2：For the Raman spectrogram of the carbon film prepared in the embodiment of the present invention 1, it can be seen that typical D peaks (1200 occur
~1450cm-1) and G peaks (1500~1700cm-1) illustrate to add biomass derived Carbonaceous mesophase can be in lower temperature and relatively low
The preparation of carbon film is carried out under voltage.
Fig. 3：For x-ray photoelectron (XPS) spectrogram of the carbon film prepared in the embodiment of the present invention 1, it can be seen that allusion quotation occur
The sp of type2Hydridization (284.4eV) and sp3Hydridization (285eV), illustrate that addition biomass derived Carbonaceous mesophase can be in lower temperature
With the preparation that carbon film is carried out under low voltage.
Fig. 4：To prepare the when m- voltage relationship figure of carbon film in the embodiment of the present invention 1, illustrate carbon film can be achieved under low-voltage
Preparation.
Fig. 5：To prepare the when m- voltage relationship figure of carbon film in the embodiment of the present invention 2, a certain amount of lead is added as seen from the figure
After electric salt, deposition voltage is decreased obviously, and illustrates that after adding conducting salt the electrical conductivity of electrolyte can be improved.
Fig. 6：For the SEM photograph of the carbon film prepared in the embodiment of the present invention 2.
Fig. 7：For the SEM photograph of the carbon film prepared in the embodiment of the present invention 3.
Fig. 8：For the SEM photograph of the carbon film prepared in the embodiment of the present invention 4.
Fig. 9：For in the embodiment of the present invention 7 preparation carbon film SEM photograph.
Embodiment
Before the specific embodiment of the invention is further described, it should be appreciated that protection scope of the present invention is not limited to down
State specific specific embodiment；It is also understood that the term used in the embodiment of the present invention is specific specific in order to describe
Embodiment, the protection domain being not intended to be limiting of the invention.The test method of unreceipted actual conditions in the following example,
Generally according to normal condition, or the condition proposed by according to each manufacturer.
When embodiment provides number range, it should be appreciated that except non-invention is otherwise noted, two ends of each number range
Any one numerical value can be selected between point and two end points.Unless otherwise defined, in the present invention all technologies for using and
Scientific terminology is identical with the meaning that those skilled in the art of the present technique are generally understood that.Except used in embodiment specific method, equipment,
Outside material, according to grasp of the those skilled in the art to prior art and the record of the present invention, it can also use and this
Any method, equipment and the material of the similar or equivalent prior art of method, equipment described in inventive embodiments, material come real
The existing present invention.
Biomass derived Carbonaceous mesophase used in the present invention is public in can using China Patent No. as CN 1421477A patent
What the preparation method opened obtained.
Specifically, biomass derived Carbonaceous mesophase used is prepared using following method in embodiment.
Preparation process：
1) using biomass resource material particle, aldehydes matter and the concentrated sulfuric acid as reaction raw materials, carried out at 100~300 DEG C
Modified-reaction, obtain modified-reaction product；
2) gained modified-reaction product in step 1) is added into water agitator treating, filtering drying, obtains powder body material；
3) powder body material obtained in step 2) is heat-treated at 100~400 DEG C or microwave treatment, you can described in acquisition
Biomass derived Carbonaceous mesophase.
Further, in step 1), the average grain diameter of the biomass resource material particle is in below 1cm；More preferably, institute
The average grain diameter for stating biomass resource material particle is less than 1mm.Preferably, the reaction time of step 1) is 0.3~3 hour.
Further, in step 1), the biomass resource material particle accounts for 14~80wt.%, aldehydes matter account for 14~
65wt.%, the concentrated sulfuric acid account for 1.8-25wt.%；More preferably, the biomass resource material particle accounts for 40~75wt%, phenolic material
Matter accounts for 20~50wt.%, and the concentrated sulfuric acid accounts for 2~15wt.%.
Biomass resource material may be selected from following any one or more：Containing in the natural polymers such as cellulose, lignin
At least one natural material and/or its discarded object；Each analog derivative of the natural material and/or discarded object；Cellulose
Or each analog derivative and its mixture of lignin.
The biomass resource material may be selected from the one or more in following material：Timber, wood chip, straw, rice husk, water
Pomace, fruit core, leaf, cereal epidermis, waste paper, waste wood wood, straw, lignin sulphur hydrochlorate, alkali lignin etc..
Preferably, the aldehydes matter is phenol.
Preferably, the time of heat treatment or microwave treatment is 0.5~3h in step 3).Microwave can use the moderate heat of micro-wave oven
Wave band above.
Using the above method, it is prepared for respectively with timber, wood chip, straw, rice husk, marc, fruit core, leaf, cereal table
Skin, waste paper, waste wood wood, straw, lignin sulphur hydrochlorate, the biomass derived carbonaceous mesophase that alkali lignin is biomass resource material
Phase.
Carbon film (being free of conducting salt) is electroplated on the electro-conductive glass ITO of embodiment 1
First, electrolyte is prepared：
Under conditions of stirring, 0.001g biomass derived Carbonaceous mesophase is dissolved in 100mL ethanol, obtains concentration
For 0.01g/L interphase solution A；As electrolyte.
Then, plating is carried out using the electrolyte prepared and prepares carbon film：
(1) ITO matrixes are cleaned by ultrasonic 5min in acetone, then alcohol washes 1min, drying is stand-by；
(2) pretreated ITO matrixes are put into the electrolyte prepared and electroplated, using the side of pulse plating
Formula, the operation temperature of plating is 50 DEG C, electroplating time 5min, frequency 1KHz, dutycycle 50%, and current density is
0.5A/dm2；
(3) sample is taken out after the completion of electroplating, deionized water rinsing dries up after absolute ethyl alcohol is cleaned by ultrasonic, and obtains finished product.
The SEM photograph of prepared carbon film is shown in Fig. 1.From macrograph (Fig. 1 (a)), it can be seen that, coating surface is more uniform
It is smooth, it is made up of spheric granules；Partial enlargement be can see (Fig. 1 (b)), and film layer is stacked by Multi-layer spherical particle and formed, and
Coupled between grain by " sintering neck ", cross-hatching test shows that coating is well combined with matrix.
The Raman spectrogram of prepared carbon film is shown in Fig. 2.It can be seen that the typical D peaks of Raman spectrogram appearance (1200~
1450cm-1, represent diamond sp3The tetrahedral structure of key or the sp of hydridization defect2Key) and G peaks (1500~1700cm-1, generation
Table graphite sp2The plane tetrahedral structure of key).
The x-ray photoelectron spectrogram of prepared carbon film is shown in Fig. 3.It can be seen that x-ray photoelectron (XPS) spectrogram (Fig. 3
(b)) there is typical sp2Hydridization (284.4eV) and sp3Hydridization (285eV), illustrate to make using biomass derived Carbonaceous mesophase
For carbon source, the preparation of carbon film can be achieved.
Voltage changes with time as shown in fig. 4, it can be seen that deposition voltage maintains in electrodeposition process during electro-deposition
Within 30V, illustrate to may be implemented in as carbon source using biomass derived Carbonaceous mesophase lower temperature and voltage (50 DEG C ,≤
The preparation of carbon film under 30V).
Carbon film (containing conducting salt) is electroplated on the electro-conductive glass ITO of embodiment 2
First, electrolyte is prepared：
(1) under conditions of stirring, 0.5g biomass derived Carbonaceous mesophase is dissolved in 100mL acetamides, obtained
Concentration is 5g/L interphase solution A；
(2) 0.04g sodium chloride, 0.03g potassium chloride, 0.4g sodium hydroxides are weighed respectively, are added it in (1) preparation
Between in phase solution A, 50 DEG C of stirrings of constant temperature respectively obtain sodium chloride containing 0.4g/L, 0.3g/L potassium chloride, 4g/L hydrogen to whole dissolvings
The electrolyte of sodium oxide molybdena, while comparative study is carried out as blank electrolysis liquid using the interphase solution A without conducting salt.
Then, plating is carried out using the electrolyte prepared and prepares carbon film：
(1) ITO matrixes are cleaned by ultrasonic 5min in acetone, then alcohol washes 1min, drying is stand-by；
(2) pretreated ITO matrixes are put into the electrolyte prepared and electroplated, using the side of pulse plating
Formula, the operation temperature of plating is 30 DEG C, electroplating time 30min, frequency 1KHz, dutycycle 50%, current density 1A/
dm2；
(3) sample is taken out after the completion of electroplating, deionized water rinsing dries up after absolute ethyl alcohol is cleaned by ultrasonic, and obtains finished product.
Voltage changes with time as shown in Figure 5 during electro-deposition, it can be seen that after adding a certain amount of conducting salt, deposition electricity
Pressure is decreased obviously, and illustrates that after adding conducting salt the electrical conductivity of electrolyte can be significantly improved so that electro-deposition voltage declines.Can be real
The preparation of carbon film under present lower temperature and voltage (50 DEG C ,≤10V).
The SEM photograph of prepared carbon film is as shown in Figure 6, it can be seen that after adding a certain amount of conducting salt, can also obtain
The carbon film of uniform surface, carbon film are made up of nano particle.
In addition, magnesium chloride or calcium chloride also can be selected as conducting salt, and similar effect can be obtained.
Carbon film is electroplated on the Titanium base of embodiment 3
First, electrolyte is prepared：
(1) under conditions of stirring, 0.1g biomass derived Carbonaceous mesophase is dissolved in 50mL ethanol and 50mL N, N-
In the mixed solution of dimethylformamide (DMF), the interphase solution A that concentration is 1g/L is obtained；
(2) 5g potassium acetates are weighed, are added it in the interphase solution A of (1) preparation, 50 DEG C of constant temperature is stirred to all molten
Solution, obtains the electrolyte of the potassium acetate containing 50g/L.
Then, plating is carried out using the electrolyte prepared and prepares carbon film：
(1) by Ti6Al4Matrix is polished with SiC sand paper and polished with diamond paste, and then flowing water rinses, deionized water
Cleaning, drying are stand-by；
(2) by pretreated Ti6Al4Matrix is put into the electrolyte prepared and electroplated, the side electroplated using constant current
Formula, the operation temperature of plating is 40 DEG C, electroplating time 120min, current density 3A/dm2；
(3) sample is taken out after the completion of electroplating, deionized water rinsing dries up after absolute ethyl alcohol is cleaned by ultrasonic, and obtains finished product.
The SEM photograph of prepared carbon film is as shown in Figure 7, it can be seen that the carbon film of preparation is continuously covered on matrix, table
Polygon is presented in face pattern；Cross-hatching test shows that coating is well combined with matrix.
And after adding a certain amount of conducting salt, deposition voltage is decreased obviously, illustrate substantially carry after adding conducting salt
The electrical conductivity of high electrolyte so that electro-deposition voltage declines.It may be implemented in carbon film under lower temperature and voltage (50 DEG C ,≤10V)
Preparation.
In addition, magnesium acetate also can be selected as conducting salt, and similar effect can be obtained.
Carbon film is electroplated on the silicon substrate of embodiment 4
First, electrolyte is prepared：
(1) under conditions of stirring, 1g biomass derived Carbonaceous mesophase is dissolved in 100mL ethylene glycol, obtained dense
Spend the interphase solution A for 10g/L；
(2) 2g KIs are weighed respectively, are added it in the interphase solution A of (1) preparation, and 50 DEG C of constant temperature is stirred to complete
Portion dissolves, and adds 1g Nano-meter SiO_2s2, obtain KI containing 20g/L, 10g/L Nano-meter SiO_2s2Electrolyte.
Then, plating is carried out using the electrolyte prepared and prepares carbon film：
(1) by silicon substrate in hydrofluoric acid etch 2min, then alcohol ultrasonic wave cleaning and dries up 5min, stand-by；
(2) pretreated silicon substrate is put into the electrolyte prepared and electroplated, by the way of constant pressure plating,
The operation temperature of plating is 60 DEG C, electroplating time 60min, voltage 30V；
(3) sample is taken out after the completion of electroplating, deionized water rinsing dries up after absolute ethyl alcohol is cleaned by ultrasonic, and obtains sample；
(4) sample is subjected to 550 DEG C of heat treatments, atmosphere is argon gas, time 3h, obtains finished product；
The front and rear SEM photograph of prepared carbon film heat treatment is as shown in Figure 8.It can be seen that the carbon film before heat treatment is by " burning
The spherical nanoparticle composition (Fig. 8 (a)) that knot neck " is connected；The densification that film layer becomes after heat treatment, local carbon film is then network-like,
But still can see and be made up of obvious spheric granules, (Fig. 8 (b)).
After adding a certain amount of conducting salt and additive, deposition current is always held at higher stationary value, illustrates addition
The electrical conductivity of electrolyte can be significantly improved after conducting salt, electrodeposition process is carried out continuously and healthily.It can be seen that in lower temperature
With the preparation that carbon film can be carried out under voltage (60 DEG C ,≤30V).
In addition, sodium iodide also can be selected as conducting salt, and similar effect can be obtained.
Iron plating doped carbon film on the stainless steel base of embodiment 5
First, electrolyte is prepared：
(1) under conditions of stirring, 0.8g biomass derived Carbonaceous mesophase is dissolved in 100mL methanol, obtained dense
Spend the interphase solution A for 8g/L；
(2) 1.5g sodium bromides are weighed, are added it in the interphase solution A of (1) preparation, 50 DEG C of stirrings of constant temperature to whole
Dissolving, adds 0.01g ferric acetyl acetonades, obtains sodium bromide containing 15g/L, the electrolyte of 0.1g/L ferric acetyl acetonades.
Then, plating is carried out using the electrolyte prepared and prepares Fe2O3 doping carbon film：
(1) by stainless steel base in hydrochloric acid solution electrolytic cleaned 3min, concentration of hydrochloric acid：20wt.%, current density：
1.5A/dm2, stainless steel after anode processing 1min as cathode treatment 2min is re-used as, then in alcohol ultrasonic cleaning 5min simultaneously
Drying, it is stand-by；
(2) pretreated stainless steel base is put into the electrolyte prepared and electroplated, using constant current plating
Mode, the operation temperature of plating is 55 DEG C, electroplating time 45min, current density 5A/dm2；
(3) sample is taken out after the completion of electroplating, deionized water rinsing dries up after absolute ethyl alcohol is cleaned by ultrasonic, and obtains sample；
(4) sample is subjected to 1000 DEG C of heat treatments, atmosphere is nitrogen, time 2h, obtains finished product；
A certain amount of ferric acetyl acetonade is added, the carbon film of Fe2O3 doping can be obtained.
After adding a certain amount of conducting salt and additive, deposition voltage is decreased obviously, illustrate add conducting salt after can be with bright
The aobvious electrical conductivity for improving electrolyte so that electro-deposition voltage declines.It may be implemented under lower temperature and voltage (55 DEG C ,≤20V)
The preparation of carbon film.
In addition, potassium sulfate, sodium sulphate, magnesium sulfate also can be selected can obtain similar effect as conducting salt.
Electro-coppering doped carbon film on the Copper substrate of embodiment 6
First, electrolyte is prepared：
(1) under conditions of stirring, 0.3g biomass derived Carbonaceous mesophase is dissolved in 100mL acetic acid, obtained dense
Spend the interphase solution A for 3g/L；
(2) 1.2g sodium acetates are weighed, are added it in the interphase solution A of (1) preparation, 50 DEG C of stirrings of constant temperature to whole
Dissolving, adds 0.6g cupric perchlorates, obtains sodium acetate containing 12g/L, the electrolyte of 6g/L cupric perchlorates.
Then, plating is carried out using the electrolyte prepared and prepares Copper-cladding Aluminum Bar carbon film：
(1) by Copper substrate, etch 2min, then alcohol ultrasonic wave cleaning and are blown 5min in 65wt.% salpeter solution
It is dry, it is stand-by；
(2) pretreated Copper substrate is put into the electrolyte prepared and electroplated, by the way of pulse plating,
The operation temperature of plating is 45 DEG C, electroplating time 120min, frequency 2KHz, dutycycle 30%, current density 4A/
dm2；
(3) sample is taken out after the completion of electroplating, deionized water rinsing dries up after absolute ethyl alcohol is cleaned by ultrasonic, and obtains sample.
(4) sample is subjected to 750 DEG C of heat treatments, atmosphere is nitrogen, time 1h, obtains finished product；
A certain amount of cupric perchlorate is added, the C film of Copper-cladding Aluminum Bar can be obtained.
After adding a certain amount of conducting salt and additive, deposition voltage is decreased obviously, illustrate add conducting salt after can be with bright
The aobvious electrical conductivity for improving electrolyte so that electro-deposition voltage declines.It may be implemented under lower temperature and voltage (45 DEG C ,≤15V)
The preparation of carbon film.
Carbon film is electroplated on the titania nanotube matrix of embodiment 7
First, electrolyte is prepared：
(1) under conditions of stirring, 0.6g biomass derived Carbonaceous mesophase is dissolved in 100mL methanol and ethanol
(volume ratio of methanol and ethanol is 1：4) the interphase solution A that concentration is 6g/L, is obtained；
(2) 0.02g potassium chloride is weighed, is added it in the interphase solution A of (1) preparation, 50 DEG C of constant temperature is stirred to complete
Portion dissolves, and obtains the electrolyte of the potassium chloride containing 0.2g/L.
Then, plating is carried out using the electrolyte prepared and prepares carbon film：
(1) titania nanotube matrix is cleaned by ultrasonic 5min in deionized water, then alcohol washes 1min, dried up
It is stand-by；
(2) titania nanotube matrix is put into the electrolyte prepared and electroplated, the side electroplated using constant pressure
Formula, the operation temperature of plating is 55 DEG C, electroplating time 10min, voltage 1.5V；
(3) sample is taken out after the completion of electroplating, deionized water rinsing dries up after absolute ethyl alcohol is cleaned by ultrasonic, and obtains finished product.
The SEM photograph of prepared carbon film is as shown in Figure 9.It can be seen that cover one on titania nanotube surface
A thin layer of carbon film.
After adding a certain amount of conducting salt and additive, deposition current is always held at higher stationary value, illustrates addition
The electrical conductivity of electrolyte can be significantly improved after conducting salt, electrodeposition process is carried out continuously and healthily.It may be implemented in compared with low temperature
The preparation of carbon film under degree and voltage (55 DEG C ,≤1.5V).
The carbon film that electronickelling is adulterated on the magnesium matrix of embodiment 8
First, electrolyte is prepared：
(1) under conditions of stirring, 0.9g biomass derived Carbonaceous mesophase is dissolved in 100mL acetamides, obtained
Concentration is 9g/L interphase solution A；
(2) 4g potassium nitrate is weighed, is added it in the interphase solution A of (1) preparation, 50 DEG C of constant temperature is stirred to all molten
Solution, adds 0.2g nickel acetylacetonates, obtains potassium nitrate containing 40g/L, the electrolyte of 2g/L nickel acetylacetonates.
Then, plating is carried out using the electrolyte prepared and prepares carbon film：
(1) magnesium matrix is passed through into alkaline degreasing → pickling → activation process, alkaline degreasing liquid by 50g/L sodium hydroxides and
10g/L tertiary sodium phosphates form；Pickle is made up of the 180g/L dry nitric acid with 110mL/L of chromium；Activation process liquid is 385mL/L
Hydrofluoric acid solution (40%)；It is finally stand-by using deionized water rinsing, drying using flowing water cleaning 1min between each step；
(2) pretreated magnesium matrix is put into the electrolyte prepared and electroplated, by the way of constant current plating,
The operation temperature of plating is 70 DEG C, electroplating time 90min, current density 0.1A/dm2,
(3) sample is taken out after the completion of electroplating, deionized water rinsing dries up after absolute ethyl alcohol is cleaned by ultrasonic, and obtains finished product.
A certain amount of nickel acetylacetonate is added, the carbon film of nickel doping can be obtained.
After adding a certain amount of conducting salt and additive, deposition voltage is decreased obviously, illustrate add conducting salt after can be with bright
The aobvious electrical conductivity for improving electrolyte so that electro-deposition voltage declines.It may be implemented in carbon under lower temperature and voltage (70 DEG C ,≤3V)
The preparation of film.
In addition, sodium nitrate or magnesium nitrate also can be selected as conducting salt, and similar effect can be obtained.
It is described above, only presently preferred embodiments of the present invention, it is not any to the present invention in form and substantial limitation,
It should be pointed out that for those skilled in the art, on the premise of the inventive method is not departed from, can also make
Some improvement and supplement, these are improved and supplement also should be regarded as protection scope of the present invention.All those skilled in the art,
Without departing from the spirit and scope of the present invention, when made using disclosed above technology contents it is a little more
Dynamic, modification and the equivalent variations developed, it is the equivalent embodiment of the present invention；Meanwhile all substantial technologicals pair according to the present invention
The variation, modification and evolution for any equivalent variations that above-described embodiment is made, still fall within the scope of technical scheme
It is interior.
Claims (9)
1. a kind of electrolyte, organic molten described in per 1000ml containing biomass derived Carbonaceous mesophase, conducting salt and organic solvent
In agent, the conducting salt containing 0.01 gram~10 grams of the biomass derived Carbonaceous mesophase and 0.1g~50g, the conduction
Salt be selected from sodium chloride, potassium chloride, magnesium chloride, calcium chloride, potassium acetate, magnesium acetate, KI, sodium iodide, sodium bromide, sodium acetate,
Any of potassium nitrate, sodium nitrate, magnesium nitrate, potassium sulfate, sodium sulphate, magnesium sulfate or a variety of combinations.
2. electrolyte according to claim 1, it is characterised in that the organic solvent be selected from acetamide, methanol, ethanol,
Any one or more combination in acetic acid, ethylene glycol, DMF (DMF).
3. electrolyte according to claim 1, it is characterised in that also contain additive in the electrolyte.
4. electrolyte according to claim 3, it is characterised in that the additive is selected from metal salt, Organometallic closes
Any of nano particle of thing or nonmetalloid or a variety of combinations.
5. electrolyte according to claim 4, it is characterised in that in organic solvent described in per 1000mL, containing 0.1g~
10g additive.
6. the preparation method of electrolyte as described in Claims 1 to 5 any claim, it is characterised in that comprise the following steps：
(1) biomass derived carbonaceous mesophase is added in organic solvent by proportioning, dissolves, obtain interphase organic solution；
When in the electrolyte, when containing conducting salt but not containing additive, methods described, on the basis of including step (1),
Also include step：
(2) conducting salt is added in gained interphase organic solution into step (1) by proportioning, dissolves, obtain mixed liquor, you can as
Electrolyte；
When in the electrolyte, also containing conducting salt and during additive, methods described is also wrapped on the basis of including step (1)
Include step：
(2) additive is added in gained interphase organic solution into step (1) by proportioning, dissolves, obtain mixed liquor；Then by matching somebody with somebody
Than adding conducting salt into gained mixed liquor, dissolving, you can as electrolyte.
7. purposes of the electrolyte in field of electroplating prepares carbon film as described in Claims 1 to 5 any claim.
8. a kind of electro-plating method, comprises the following steps：
(1) treatment before plating：Matrix material is handled according to the preprocess method in conventional plating process；
(2) pretreated matrix material is put into the electrolyte as described in Claims 1 to 5 any claim and carries out electricity
Plating；
(3) sample is taken out, drying is rinsed, produces carbon film.
9. according to the method for claim 8, it is characterised in that methods described also includes step (4), to obtained by step (3)
Carbon film is heat-treated, cooling.
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|---|---|---|---|---|
| JP2000226691A (en) * | 1999-02-05 | 2000-08-15 | Toyo Kohan Co Ltd | Production of surface treated steel sheet and surface treated steel sheet |
| CN101381882A (en) * | 2008-03-28 | 2009-03-11 | 北京化工大学 | Method for preparing diamond-like film by low voltage liquid phase electrodeposit |
| CN102776510A (en) * | 2012-08-20 | 2012-11-14 | 上海交通大学 | Method for preparing diamond carbon membrane on stainless steel surface |
| CN103031581A (en) * | 2012-02-27 | 2013-04-10 | 湖南理工学院 | Method of preparing multi-element carbide film through electrodeposition of liquid phase plasmas |
| CN104638255A (en) * | 2015-02-02 | 2015-05-20 | 斌源材料科技（上海）有限公司 | Lithium titanate/carbon composite material and method for preparing material |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000226691A (en) * | 1999-02-05 | 2000-08-15 | Toyo Kohan Co Ltd | Production of surface treated steel sheet and surface treated steel sheet |
| CN101381882A (en) * | 2008-03-28 | 2009-03-11 | 北京化工大学 | Method for preparing diamond-like film by low voltage liquid phase electrodeposit |
| CN103031581A (en) * | 2012-02-27 | 2013-04-10 | 湖南理工学院 | Method of preparing multi-element carbide film through electrodeposition of liquid phase plasmas |
| CN102776510A (en) * | 2012-08-20 | 2012-11-14 | 上海交通大学 | Method for preparing diamond carbon membrane on stainless steel surface |
| CN104638255A (en) * | 2015-02-02 | 2015-05-20 | 斌源材料科技（上海）有限公司 | Lithium titanate/carbon composite material and method for preparing material |
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