CN104064364B - Preparation method of graphene for super capacitors for lead-carbon batteries - Google Patents
Preparation method of graphene for super capacitors for lead-carbon batteries Download PDFInfo
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- CN104064364B CN104064364B CN201410269292.9A CN201410269292A CN104064364B CN 104064364 B CN104064364 B CN 104064364B CN 201410269292 A CN201410269292 A CN 201410269292A CN 104064364 B CN104064364 B CN 104064364B
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- graphene
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- hydrazine hydrate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a preparation method of graphene for super capacitors for lead-carbon batteries and belongs to the technical field of lead-acid storage battery manufacturing. The preparation method is characterized by comprising the steps of compounding a GO through a Hummers method, restoring the GO through hydrazine hydrate and ammonium hydroxide to prepare the graphene for the super capacitors, refining the graphene through centrifugal separation and vacuum filtration methods, and assembling graphene film obtained by filtration into symmetrical capacitors with specific capacitance reaching up to 395F/g. By adding the graphene for the super capacitors into negative electrode diachylon of the lead-carbon batteries, charge-discharge suffertibility of large current and cycle performance under part of states of charge of the batteries can be improved remarkably, sulfation of surfaces of electrodes is inhibited, and therefore, the batteries have high capacity and long cycle life.
Description
Technical field
The present invention relates to a kind of preparation method of the electrochemical capacitance Graphene for lead carbon battery, belong to lead-acid accumulator and make
Technical field.
Background technology
Lead-acid battery have raw material sources wide and be conveniently easy to get, low cost, safe, stable performance and recyclable
Using many advantages, such as, be developed to today still in occupation of the considerable market share.With scientific and technological progress and development, each row
Industry proposes new requirement to lead-acid accumulator, and improving specific capacity and cycle life, reduction product weight is urgent need to resolve
Problem.Lead carbon battery is by adding a certain amount of characteristic Carbon Materials in acid accumulator negative pole lead, and the height using Carbon Materials is led
Electrically and capacitance characteristic, improve the ability that pole plate accepts instantaneous large-current, suppress polar board surface sulfation, improve active substance
Utilization rate and discharge and recharge ability to accept, significantly improve the cycle life of high magnification partial state of charge.
What lead carbon battery was commonly used the active charcoal of charcoal additive, white carbon black, carbon nanofibers, graphite and CNT etc..Reason
The charcoal additive thought should have very high specific surface area and electric conductivity, plays its capacitance characteristic in charge and discharge process, buffers wink
Between high current；Have concurrently affine with lead plaster good, dispersibility is high, and strong in electrochemical environment stability inferior simultaneously.Graphene is
The nearly carbon family two-dimensional material risen, has numerous excellent specific properties, specific surface area and electrical conductivity are very high, good stability, is a kind of
Ideal charcoal additive.Graphene is initially the carbon monoatomic layer being stripped down from graphite using mechanical stripping method, should
The Graphene purity that method obtains is high, defect is few, but its preparation condition harsh it is difficult to realize mass production, and price is held high
Expensive.Laboratory prepares Graphene using oxide-reduction method mostly, first with strong oxidizer by graphite oxidation, by chemical interactions
Peel off graphite, then graphite oxide reduction is obtained Graphene.But, the oxy radical that oxidation reaction introduces and in-plane defects are difficult
To eliminate, its end product quality is difficult to control to, and concordance is poor.How to realize the high-quality of Graphene and finished product concordance is one
Far reaching problem.
Content of the invention
It is an object of the invention to overcoming the deficiencies in the prior art, provide a kind of quality that can improve Graphene and finished product one
The preparation method of the electrochemical capacitance Graphene for lead carbon battery of cause property.
The technical solution adopted in the present invention is as follows: a kind of preparation method of the electrochemical capacitance Graphene for lead carbon battery,
It is characterized in that go is synthesized using hummers method, reduction go is combined by hydrazine hydrate and ammonia, is taken out with centrifugation and vacuum
The Methods For Purification of filter, is finally obtained electrochemical capacitance Graphene, and above-mentioned go refers to graphene oxide.
Further scheme is: described hummers method synthesis go step is: (1), close toward filling 150～200ml
0o3.5～4.0g sodium nitrate and 4～6g expanded graphite is once added in c ice strong sulfuric acid response device, continuous stirring reaction 2.5～
4h；(2), it is slowly added to 20～25g potassium permanganate, control reactor temperature to be less than 20oC, is sufficiently stirred for reacting 10～14h；
(3), add 400～800 ml 4～6 wt.% dilution heat of sulfuric acid to stir 20～30 min, add 40～60 g 30 wt.%
Hydrogen peroxide stirs 30～45 min；(4), washed with excessive 30 wt.% sulphuric acid/1 wt.% mixed solution of hydrogen peroxide centrifugations
Wash, be finally equal to 7 with water centrifuge washing to supernatant ph, obtain light yellow go dispersion liquid.
Described hydrazine hydrate and ammonia joint method of reducing are: take go dispersion liquid, sequentially add a certain amount of ammonia and water
Close hydrazine solution, reduce under the conditions of water bath with thermostatic control, concentration of hydrazine hydrate is 35～45 wt.%, ammonia concn is 30～40 wt.%,
Hydrazine hydrate is 1:100～140 with the quality proportioning of go dispersion liquid, quality proportioning 1:10～25 of ammonia and go dispersion liquid, water-bath
Temperature is 90～100 DEG C, and the water-bath time is 1～1.5h.
In described purification process, vacuum filtration pressure is 5～10kpa, and centrifugation rotating speed is 2000～10000r/
Min, disengaging time is 5～10min.
The electrochemical capacitance Graphene quality of technical scheme preparation provided by the present invention is high, and capacitive property is good, and manufacturing process
Simply, specification, controlled, is suitable to mass production.Test shows, prepared electrochemical capacitance Graphene is used for lead carbon battery, Ke Yixian
Write the cycle performance improving under battery high current charge-discharge suffertibility and partial state of charge, the sulfate of suppression electrode surface
Change, make battery have high power capacity and long circulation life concurrently.
Brief description
Fig. 1 is the transmission electron microscope picture of electrochemical capacitance Graphene；
Fig. 2 is with the constant current charge-discharge curve of the symmetric capacitor of graphene film composition.
Specific embodiment
The present invention is further described below in conjunction with the accompanying drawings.
The preparation method of electrochemical capacitance Graphene being used for lead carbon battery in the present embodiment is it is characterised in that adopt hummers
Method synthesizes go, combines reduction go by hydrazine hydrate and ammonia, and is obtained super with the Methods For Purification of centrifugation and vacuum filtration
Electric capacity Graphene.
The hummers method of synthesis go, synthesis step is: (1), toward filling 175ml close to 0oIn c ice strong sulfuric acid response device
Once add 3.75g sodium nitrate and 5g expanded graphite, continuous stirring reacts 3h；(2), it is slowly added to 22.5g potassium permanganate, control
Reactor temperature is less than 20oC, is sufficiently stirred for reacting 12h；(3), add 500ml5wt.% dilution heat of sulfuric acid stirring 30min, then
50g30 wt.% hydrogen peroxide is added to stir 30 min；(4), with 30wt.% sulphuric acid/1wt.% mixed solution of hydrogen peroxide centrifugation
Washing, finally with water centrifuge washing to supernatant ph=7, obtains light yellow go dispersion liquid.
Reduction go is combined with hydrazine hydrate and ammonia, its operating procedure is: takes above-mentioned prepared go dispersion liquid, sequentially adds one
Quantitative ammonia and hydrazine hydrate solution, reduce under the conditions of water bath with thermostatic control and Graphene are obtained.Concentration of hydrazine hydrate is 40wt.%, ammonia
Water concentration is 35wt.%, and hydrazine hydrate is 1:120 with the quality proportioning of go, quality proportioning 1:20 of ammonia and go, and bath temperature is
90～100oC, the water-bath time is 1h.The purification in later stage adopts centrifugation and vacuum filtration, and concrete operation step is such as
Under: (1), by the mixed liquor standing after water-bath, pour out the supernatant；(2), the pasty state settling down is added pure water with 6000r/
The time centrifuge washing (i.e. centrifugation) of the rotating speed of min and 8min is equal to 7 to washing liquid ph；(3), pass through vacuum filtration by graphite
Alkene makes the thin film that thickness is about 2mm, and vacuum filtration pressure is 5～10 kpa.
Gained Graphene, as the test specimens of transmission electron microscope, is baked to content and the specific surface of determination of water Graphene
Long-pending.Fig. 1 is the transmission electron microscope picture of Graphene, and the Graphene combining reduction with hydrazine hydrate and ammonia has obvious laminated structure,
Compound with regular structure, thickness is homogeneous.The nitrogen adsorption desorption curve of the Graphene sample after drying, calculates its ratio according to bet formula
Surface area is 1169 m2/g.Thus infer, the Graphene of the method preparation has 2～5 carbon atomic layers, and concordance is preferable.
The graphene film that sucking filtration is obtained is assembled in and is assembled into symmetrical capacitor under atmospheric environment, and collector is aluminum
Paper tinsel, electrolyte is 6m potassium hydroxide solution.Fig. 2 is the symmetric capacitor constant current charge-discharge diagram being assembled by graphene film, charge and discharge
Potential range is 0～1v, according tocs= 4i/[(δu/δt)·m] calculate ratio electric capacity, under 0.1a/g electric current density, it is than electricity
Hold and be up to 395 f/g.
According to drying the Graphene content that moisture calculates, Graphene is added to lead carbon battery by 1.5-3% in mass ratio
In cathode lead plaster, found by blank, add the battery specific capacity of electrochemical capacitance Graphene and specific power is significantly improved,
Significantly enhance cycle performance under battery high current charge-discharge suffertibility and partial state of charge it is adaptable to power and energy storage
In field, have broad application prospects.
Claims (2)
1. a kind of preparation method of the electrochemical capacitance Graphene for lead carbon battery, synthesizes go using hummers method, by hydration
Hydrazine and ammonia combine reduction go, with the Methods For Purification of centrifugation and vacuum filtration, electrochemical capacitance Graphene, above-mentioned go are finally obtained
Refer to graphene oxide it is characterised in that described hummers method synthesis go step is: (1), toward filling 150～200ml
Close to 0o3.5～4.0g sodium nitrate and 4～6g expanded graphite, continuous stirring reaction 2.5 is once added in c ice strong sulfuric acid response device
～4h；(2), it is slowly added to 20～25g potassium permanganate, control reactor temperature to be less than 20oC, it is sufficiently stirred for reacting 10～
14h；(3), add 400～800 ml 4～6 wt.% dilution heat of sulfuric acid to stir 20～30 min, add 40～60 g 30
Wt.% hydrogen peroxide stirs 30～45 min；(4), with excessive 30 wt.% sulphuric acid/1 wt.% mixed solution of hydrogen peroxide centrifugations
Washing, is finally equal to 7 with water centrifuge washing to supernatant ph, obtains light yellow go dispersion liquid；Described hydrazine hydrate and ammonia
Joint method of reducing is: takes go dispersion liquid, sequentially adds a certain amount of ammonia and hydrazine hydrate solution, under the conditions of water bath with thermostatic control also
Former, concentration of hydrazine hydrate is 35～45 wt.%, and ammonia concn is 30～40 wt.%, and hydrazine hydrate with the quality proportioning of go dispersion liquid is
Quality proportioning 1:10～25 of 1:100～140, ammonia and go dispersion liquid, bath temperature is 90～100 DEG C, the water-bath time
For 1～1.5h.
2. the preparation method of the electrochemical capacitance Graphene for lead carbon battery according to claim 1 is it is characterised in that described
Purification process in, vacuum filtration pressure be 5～10 kpa, centrifugation rotating speed be 2000～10000r/min, disengaging time
For 5～10min.
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| CN107005068B (en) | 2014-11-13 | 2021-05-04 | Zapgo公司 | Battery charger |
| GB2544775B (en) | 2015-11-26 | 2021-07-21 | Zapgo Ltd | Portable electronic device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102275908A (en) * | 2011-07-07 | 2011-12-14 | 中南大学 | Preparation method of graphene material |
| CN103183334A (en) * | 2013-03-11 | 2013-07-03 | 上海理工大学 | Preparation method of size controllable grapheme |
| CN103342904A (en) * | 2013-07-29 | 2013-10-09 | 上海理工大学 | Method for preparing water-soluble graphene by titanate coupling agent modification process |
| CN103496691A (en) * | 2013-09-13 | 2014-01-08 | 山东聊城鲁西化工集团有限责任公司 | Preparation method of graphene dispersion liquid |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102275908A (en) * | 2011-07-07 | 2011-12-14 | 中南大学 | Preparation method of graphene material |
| CN103183334A (en) * | 2013-03-11 | 2013-07-03 | 上海理工大学 | Preparation method of size controllable grapheme |
| CN103342904A (en) * | 2013-07-29 | 2013-10-09 | 上海理工大学 | Method for preparing water-soluble graphene by titanate coupling agent modification process |
| CN103496691A (en) * | 2013-09-13 | 2014-01-08 | 山东聊城鲁西化工集团有限责任公司 | Preparation method of graphene dispersion liquid |
Non-Patent Citations (1)
| Title |
|---|
| 石墨烯及其典型聚合物纳米复合材料的制备方法、结构与机理研究;包晨露;《中国博士学位论文库》;20130115;8页第2段至第9页第3段、第17页第1段至第19页第1段、80页第2段 * |
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