CN1594076A - Process for preparing expanded graphite - Google Patents
Process for preparing expanded graphite Download PDFInfo
- Publication number
- CN1594076A CN1594076A CN 200410027920 CN200410027920A CN1594076A CN 1594076 A CN1594076 A CN 1594076A CN 200410027920 CN200410027920 CN 200410027920 CN 200410027920 A CN200410027920 A CN 200410027920A CN 1594076 A CN1594076 A CN 1594076A
- Authority
- CN
- China
- Prior art keywords
- graphite
- preparation
- reaction soln
- reactive tank
- expansible
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Carbon And Carbon Compounds (AREA)
- Inert Electrodes (AREA)
Abstract
The invention provides a process for preparing expanded graphite which comprises the steps of, (1) dispensing crystaline flake graphite between the parallel plate electrodes in the reaction tank, (2) applying direct current to the two electrodes, holding the current to be 100-600 mA, (3) controlling reaction liquid impedance, holding the voltage between the two electrodes to 50-250V, (4) taking out the oxygenized graphite and washing with water, drying at 30-120 deg. C.
Description
Technical field
The present invention relates to a kind of Preparation of Expansible Graphite method, the preparation method of electrophoretic method intercalation in particularly a kind of expansible black lead preparation process.
Background technology
Because the carbon atom of natural graphite has the netted plane of hexagonal overlay structure, interlayer when the preparation expansible black lead, adopts manual method with weak Van der Waals force combination, inserts foreign atom, ion, molecule in graphite layers, forms compound between graphite layers.Part intercalation compound thermal degradation, moment becomes gas and loss, produces tens times of expansions to hundred times at graphite crystal C axle, and makes expanded graphite.Mechanical workouts such as the expanded graphite process rolls can be made soft graphite, are widely used in sealing material, sorbing material or shielding material etc.
Now, the Preparation of Expansible Graphite method except that chemical method, also has electrochemical method.Chemical process is by carrying out the oxidation intercalation with some such as strong oxidizers such as sulfuric acid, nitric acid; And electrochemical method is that graphite is placed electrolytic bath, feeds pulsed current by two electrodes, and carries out anodic oxidation treatment.The shortcoming that above-mentioned preparation method exists is: 1, in the chemical process since adopt mostly be strong acid as oxygenant, make in the product inevitably residual sulfur, nitrogen.And the severe corrosive of residual sulphur has limited expanded graphite aspect sealing material and otherwise use to a great extent.As patent publication No.: the disclosed method of CN 1096767A is a medium with sulfuric acid, is oxygenant with the ammonium persulphate, patent publication No.: the disclosed method of CN 85103917A, and use nitric acid and sulfuric acid to be oxygenant.2, in the electrochemical method, need logical reversible circulation to carry out cathodic reduction after the anodic oxidation, the equipment complexity, as the equipment among the disclosed preparation method of patent publication No.: CN1061388A, the battery lead plate area is big, and anode side is equipped with the infiltration frame.And present electrochemical method still adopts strong acid as electrolytic medium mostly, and the power consumption height, length consuming time.
The aspect content
The purpose of this invention is to provide a kind of Preparation of Expansible Graphite method, the technical problem that solve is to prepare no sulphur expanded graphite fast.
The present invention is by the following technical solutions: a kind of Preparation of Expansible Graphite method may further comprise the steps: (1) is placed on crystalline flake graphite between the battery lead plate parallel in the reactive tank, graphite is soaked in the reaction solution, and makes itself and reaction solution keep well contacting; (2) add galvanic current between two electrodes, holding current is 100 to 600 milliamperes; (3) impedance of control reaction solution keeps between two electrodes voltage 50 to 250V; (4) graphite after the oxidation takes out washing, carries out drying under 30～120 ℃, makes expansible black lead.
Angle between the lamella direction of crystalline flake graphite of the present invention and the normal direction of battery lead plate is not more than 15 °.
The lamella direction of crystalline flake graphite of the present invention is consistent with battery lead plate planar normal direction.
Reaction solution of the present invention is the mixing solutions of organic acid and nitric acid.
Basic invention organic acid can adopt diacetyl oxide, acetate or propionic acid.
Organic acid of the present invention and nitric acid mixing solutions are organic acid, concentrated nitric acid, KMnO
4And FeCl
3Mixed solution, its mass ratio is an organic acid: concentrated nitric acid: KMnO
4: FeCl
3=8～5: 1: 0.1: 0.1.
Reactive tank of the present invention places ultrasonator, and ultrasonic concussion is 3 to 30 minutes under the condition that keeps voltage between two electrodes.
The dried expansible black lead of the present invention can make expanded graphite 600 to 1100 ℃ of pyroprocessing.
The present invention compared with prior art, adopt electrophoresis intercalation technology to prepare expanded graphite, crystalline flake graphite is positioned in the reactive tank perpendicular to battery lead plate, under the effect of electrical forces, make foreign peoples's ion, under the effect of electrical forces, do directed swimming, thereby make inset enter into graphite layers fast and form compound between graphite layers, utilize organic acid to be reaction medium, the expanded graphite behind high temperature puffing, no sulphur content, and low nitrogen has good allowance for expansion, thereby finished product has lower corrodibility, equipment is simple, and the finished product rate is also higher.
Description of drawings
Fig. 1 is a reaction unit synoptic diagram of the present invention.
Embodiment
Below in conjunction with drawings and Examples the utility model is described in further detail.
As shown in Figure 1, the electrophoretic method of the expansible black lead that uses among the present invention prepares equipment, comprise following a few part: the reactive tank 1 that fills intercalation thing reaction soln, the nickel electrode plate 2 that parallels is equipped with in both sides in reactive tank 1, battery lead plate 2 is of a size of 50 * 40 millimeters, pending natural flake graphite 3 is folded up in slide glass 4 central authorities, and natural flake graphite 3 directions are vertical with parallel electrode plate 2 directions, or be not more than 15 the degree, and keep natural flake graphite 3 to have preferably contacting, again reactive tank is placed ultrasonator with reaction soln.The DYY-8B type bistable electrophoresis apparatus 5 that direct supply of the present invention adopts Liuyi Instruments Plant, Beijing to produce.
The electrophoretic method of expansible black lead of the present invention prepares equipment, mainly be to form uniform electrochemical field in parallel electrode plate central authorities, and the natural flake graphite pending in this electrochemical field that guarantees of trying one's best has identical reaction conditions, and natural flake graphite vertically is placed on two parallel electrode plate central authorities, be in order to make the natural flake graphite in-plane consistent with direction of an electric field, and the feasible easier graphite layers that enters into of ion of inserting, add ultrasonic concussion and be owing to can cause certain concentration difference in the process of reaction, and ultrasonic concussion can make that to react energy even, the carrying out that continues.
Example one: 1, preparation reaction soln are pressed diacetyl oxide: concentrated nitric acid: KMnO
4: FeCl
3=5: 1: 0.1: 0.1 ratio preparation; 2, natural flake graphite is folded up in slide glass, and vertically be positioned in the two interior electrodes of reactive tank, keep graphite to have preferably and contact with reaction soln; 3, reactive tank is placed ultrasonator; 4, perfectly straight stream current stabilization electric current, holding current is 100 milliamperes; 5, by the adding of control reaction soln, the voltage of controlling two electrode pads is at 50 volts, and 6, ultrasonic concussion, at room temperature, reacted 20 minutes; 7, the graphite after handling is through washing, and dry down at 60 ℃; 8, dried expansible black lead is 920 ℃ pyroprocessing, the preparation expanded graphite.The expansion multiple of prepared expanded graphite is about 35 times, the content of no sulphur in the product.
Example two: 1, preparation reaction soln are pressed diacetyl oxide: concentrated nitric acid: KMnO
4: FeCl
3=5: 1: 0.1: 0.1 ratio preparation; 2, natural flake graphite is folded up in slide glass, and vertically be positioned in the two interior electrodes of reactive tank, keep graphite to have preferably and contact with reaction soln; 3, reactive tank is placed ultrasonator; 4, perfectly straight stream current stabilization electric current, holding current is 200 milliamperes; 5, by the adding of control reaction soln, the voltage of controlling two electrode pads is at 50 volts, and 6, ultrasonic concussion, at room temperature, reacted 20 minutes; 7, the graphite after handling is through washing, and dry down at 60 ℃; 8, dried expansible black lead is 920 ℃ pyroprocessing, the preparation expanded graphite.The expansion multiple of prepared expanded graphite is about 70 times, the content of no sulphur in the product.
Example three: 1, preparation reaction soln are pressed diacetyl oxide: concentrated nitric acid: KMnO
4: FeCl
3=5: 1: 0.1: 0.1 ratio preparation; 2, natural flake graphite is folded up in slide glass, and vertically be positioned in the two interior electrodes of reactive tank, keep graphite to have preferably and contact with reaction soln; 3, reactive tank is placed ultrasonator; 4, perfectly straight stream current stabilization electric current, holding current is 300 milliamperes; 5, by the adding of control reaction soln, the voltage of controlling two electrode pads is at 50 volts, and 6, ultrasonic concussion, at room temperature, reacted 20 minutes; 7, the graphite after handling is through washing, and dry down at 60 ℃; 8, dried expansible black lead is 920 ℃ pyroprocessing, the preparation expanded graphite.The expansion multiple of prepared expanded graphite is about 220 times, the content of no sulphur in the product.
Example four: 1, preparation reaction soln are pressed diacetyl oxide: concentrated nitric acid: KMnO
4: FeCl
3=5: 1: 0.1: 0.1 ratio preparation; 2, natural flake graphite is folded up in slide glass, and vertically be positioned in the two interior electrodes of reactive tank, keep graphite to have preferably and contact with reaction soln; 3, reactive tank is placed ultrasonator; 4, perfectly straight stream current stabilization electric current, holding current is 400 milliamperes; 5, by the adding of control reaction soln, the voltage of controlling two electrode pads is at 50 volts, and 6, ultrasonic concussion, at room temperature, reacted 20 minutes; 7, the graphite after handling is through washing, and dry down at 60 ℃; 8, dried expansible black lead is 920 ℃ pyroprocessing, the preparation expanded graphite.The expansion multiple of prepared expanded graphite is about 238 times, the content of no sulphur in the product.
Example five: 1, preparation reaction soln are pressed diacetyl oxide: concentrated nitric acid: KMnO
4: FeCl
3=5: 1: 0.1: 0.1 ratio preparation; 2, natural flake graphite is folded up in slide glass, and vertically be positioned in the two interior electrodes of reactive tank, keep graphite to have preferably and contact with reaction soln; 3, reactive tank is placed ultrasonator; 4, perfectly straight stream current stabilization electric current, holding current is 500 milliamperes; 5, by the adding of control reaction soln, the voltage of controlling two electrode pads is at 50 volts, and 6, ultrasonic concussion, at room temperature, reacted 20 minutes; 7, the graphite after handling is through washing, and dry down at 60 ℃; 8, dried expansible black lead is 920 ℃ pyroprocessing, the preparation expanded graphite.The expansion multiple of prepared expanded graphite is about 262 times, the content of no sulphur in the product.
Example six: 1, preparation reaction soln are pressed diacetyl oxide: concentrated nitric acid: KMnO
4: FeCl
3=5: 1: 0.1: 0.1 ratio preparation; 2, natural flake graphite is folded up in slide glass, and vertically be positioned in the two interior electrodes of reactive tank, keep graphite to have preferably and contact with reaction soln; 3, reactive tank is placed ultrasonator; 4, perfectly straight stream current stabilization electric current, holding current is 600 milliamperes; 5, by the adding of control reaction soln, the voltage of controlling two electrode pads is at 50 volts, and 6, ultrasonic concussion, at room temperature, reacted 20 minutes; 7, the graphite after handling is through washing, and dry down at 60 ℃; 8, dried expansible black lead is 920 ℃ pyroprocessing, the preparation expanded graphite.The expansion multiple of prepared expanded graphite is about 280 times, the content of no sulphur in the product.
Example seven: 1, preparation reaction soln are pressed diacetyl oxide: concentrated nitric acid: KMnO
4: FeCl
3=5: 1: 0.1: 0.1 ratio preparation; 2, natural flake graphite is folded up in slide glass, and vertically be positioned in the two interior electrodes of reactive tank, keep graphite to have preferably and contact with reaction soln; 3, reactive tank is placed ultrasonator; 4, perfectly straight stream current stabilization electric current, holding current is 300 milliamperes; 5, by the adding of control reaction soln, the voltage of controlling two electrode pads is at 150 volts, and 6, ultrasonic concussion, at room temperature, reacted 20 minutes; 7, the graphite after handling is through washing, and dry down at 60 ℃; 8, dried expansible black lead is 920 ℃ pyroprocessing, the preparation expanded graphite.The expansion multiple of prepared expanded graphite is about 272 times, the content of no sulphur in the product.
Example eight: 1, preparation reaction soln are pressed diacetyl oxide: concentrated nitric acid: KMnO
4: FeCl
3=5: 1: 0.1: 0.1 ratio preparation; 2, natural flake graphite is folded up in slide glass, and vertically be positioned in the two interior electrodes of reactive tank, keep graphite to have preferably and contact with reaction soln; 3, reactive tank is placed ultrasonator; 4, perfectly straight stream current stabilization electric current, holding current is 400 milliamperes; 5, by the adding of control reaction soln, the voltage of controlling two electrode pads is at 150 volts, and 6, ultrasonic concussion, at room temperature, reacted 20 minutes; 7, the graphite after handling is through washing, and dry down at 60 ℃; 8, dried expansible black lead is 920 ℃ pyroprocessing, the preparation expanded graphite.The expansion multiple of prepared expanded graphite is about 290 times, the content of no sulphur in the product.
Example nine: 1, preparation reaction soln are pressed diacetyl oxide: concentrated nitric acid: KMnO
4: FeCl
3=5: 1: 0.1: 0.1 ratio preparation; 2, natural flake graphite is folded up in slide glass, and vertically be positioned in the two interior electrodes of reactive tank, keep graphite to have preferably and contact with reaction soln; 3, reactive tank is placed ultrasonator; 4, perfectly straight stream current stabilization electric current, holding current is 500 milliamperes; 5, by the adding of control reaction soln, the voltage of controlling two electrode pads is at 150 volts, and 6, ultrasonic concussion, at room temperature, reacted 20 minutes; 7, the graphite after handling is through washing, and dry down at 60 ℃; 8, dried expansible black lead is 920 ℃ pyroprocessing, the preparation expanded graphite.The expansion multiple of prepared expanded graphite is about 330 times, the content of no sulphur in the product.
Example ten: 1, preparation reaction soln are pressed diacetyl oxide: concentrated nitric acid: KMnO
4: FeCl
3=5: 1: 0.1: 0.1 ratio preparation; 2, natural flake graphite is folded up in slide glass, and vertically be positioned in the two interior electrodes of reactive tank, keep graphite to have preferably and contact with reaction soln; 3, reactive tank is placed ultrasonator; 4, perfectly straight stream current stabilization electric current, holding current is 600 milliamperes; 5, by the adding of control reaction soln, the voltage of controlling two electrode pads is at 150 volts, and 6, ultrasonic concussion, at room temperature, reacted 20 minutes; 7, the graphite after handling is through washing, and dry down at 60 ℃; 8, dried expansible black lead is 920 ℃ pyroprocessing, the preparation expanded graphite.The expansion multiple of prepared expanded graphite is about 305 times, the content of no sulphur in the product.
Example 11: 1, preparation reaction soln, press diacetyl oxide: concentrated nitric acid: KMnO
4: FeCl
3=5: 1: 0.1: 0.1 ratio preparation; 2, natural flake graphite is folded up in slide glass, and vertically be positioned in the two interior electrodes of reactive tank, keep graphite to have preferably and contact with reaction soln; 3, reactive tank is placed ultrasonator; 4, perfectly straight stream current stabilization electric current, holding current is 300 milliamperes; 5, by the adding of control reaction soln, the voltage of controlling two electrode pads is at 250 volts, and 6, ultrasonic concussion, at room temperature, reacted 20 minutes; 7, the graphite after handling is through washing, and dry down at 60 ℃; 8, dried expansible black lead is 920 ℃ pyroprocessing, the preparation expanded graphite.The expansion multiple of prepared expanded graphite is about 295 times, the content of no sulphur in the product.
Example 12: 1, preparation reaction soln, press diacetyl oxide: concentrated nitric acid: KMnO
4: FeCl
3=5: 1: 0.1: 0.1 ratio preparation; 2, natural flake graphite is folded up in slide glass, and vertically be positioned in the two interior electrodes of reactive tank, keep graphite to have preferably and contact with reaction soln; 3, reactive tank is placed ultrasonator; 4, perfectly straight stream current stabilization electric current, holding current is 400 milliamperes; 5, by the adding of control reaction soln, the voltage of controlling two electrode pads is at 250 volts, and 6, ultrasonic concussion, at room temperature, reacted 20 minutes; 7, the graphite after handling is through washing, and dry down at 60 ℃; 8, dried expansible black lead is 920 ℃ pyroprocessing, the preparation expanded graphite.The expansion multiple of prepared expanded graphite is about 315 times, the content of no sulphur in the product.
Example 13: 1, preparation reaction soln, press diacetyl oxide: concentrated nitric acid: KMnO
4: FeCl
3=5: 1: 0.1: 0.1 ratio preparation; 2, natural flake graphite is folded up in slide glass, and vertically be positioned in the two interior electrodes of reactive tank, keep graphite to have preferably and contact with reaction soln; 3, reactive tank is placed ultrasonator; 4, perfectly straight stream current stabilization electric current, holding current is 500 milliamperes; 5, by the adding of control reaction soln, the voltage of controlling two electrode pads is at 250 volts, and 6, ultrasonic concussion, at room temperature, reacted 20 minutes; 7, the graphite after handling is through washing, and dry down at 60 ℃; 8, dried expansible black lead is 920 ℃ pyroprocessing, the preparation expanded graphite.The expansion multiple of prepared expanded graphite is about 285 times, the content of no sulphur in the product.
Example 14: 1, preparation reaction soln, press diacetyl oxide: concentrated nitric acid: KMnO
4: FeCl
3=5: 1: 0.1: 0.1 ratio preparation; 2, natural flake graphite is folded up in slide glass, and vertically be positioned in the two interior electrodes of reactive tank, keep graphite to have preferably and contact with reaction soln; 3, reactive tank is placed ultrasonator; 4, perfectly straight stream current stabilization electric current, holding current is 600 milliamperes; 5, by the adding of control reaction soln, the voltage of controlling two electrode pads is at 250 volts, and 6, ultrasonic concussion, at room temperature, reacted 20 minutes; 7, the graphite after handling is through washing, and dry down at 60 ℃; 8, dried expansible black lead is 920 ℃ pyroprocessing, the preparation expanded graphite.The expansion multiple of prepared expanded graphite is about 275 times, the content of no sulphur in the product.
Example 15: 1, preparation reaction soln, press diacetyl oxide: concentrated nitric acid: KMnO
4: FeCl
3=8: 1: 0.1: 0.1 ratio preparation; 2, natural flake graphite is folded up in slide glass, and make that the lamella direction of crystalline flake graphite and battery lead plate normal direction maintenance angle are 5 °, keep graphite to have preferably and contact with reaction soln; 3, reactive tank is placed ultrasonator; 4, perfectly straight stream current stabilization electric current, holding current is 180 milliamperes; 5, by the adding of control reaction soln, the voltage of controlling two electrode pads is at 50 volts, and 6, ultrasonic concussion, at room temperature, reacted 30 minutes; 7, the graphite after handling is through washing, and dry down at 60 ℃; 8, dried expansible black lead is 920 ℃ pyroprocessing, the preparation expanded graphite.The expansion multiple of prepared expanded graphite is about 70 times, the content of no sulphur in the product.
Example 16: 1, preparation reaction soln, press diacetyl oxide: concentrated nitric acid: KMnO
4: FeCl
3=6.5: 1: 0.1: 0.1 ratio preparation; 2, natural flake graphite is folded up in slide glass, and vertically be positioned in the two interior electrodes of reactive tank, keep graphite to have preferably and contact with reaction soln; 3, reactive tank is placed ultrasonator; 4, perfectly straight stream current stabilization electric current, holding current is 180 milliamperes; 5, by the adding of control reaction soln, the voltage of controlling two electrode pads is at 50 volts, and 6, ultrasonic concussion, at room temperature, reacted 30 minutes; 7, the graphite after handling is through washing, and dry down at 60 ℃; 8, dried expansible black lead is 920 ℃ pyroprocessing, the preparation expanded graphite.The expansion multiple of prepared expanded graphite is about 150 times, the content of no sulphur in the product.
Example 17: 1, preparation reaction soln, press diacetyl oxide: concentrated nitric acid: KMnO
4: FeCl
3=5: 1: 0.1: 0.1 ratio preparation; 2, natural flake graphite is folded up in slide glass, and vertically be positioned in the two interior electrodes of reactive tank, keep graphite to have preferably and contact with reaction soln; 3, reactive tank is placed ultrasonator; 4, perfectly straight stream current stabilization electric current, holding current is 180 milliamperes; 5, by the adding of control reaction soln, the voltage of controlling two electrode pads is at 50 volts, and 6, ultrasonic concussion, at room temperature, reacted 30 minutes; 7, the graphite after handling is through washing, and dry down at 60 ℃; 8, dried expansible black lead is 920 ℃ pyroprocessing, the preparation expanded graphite.The expansion multiple of prepared expanded graphite is about 200 times, the content of no sulphur in the product.
Example 18: 1, preparation reaction soln, press diacetyl oxide: concentrated nitric acid: KMnO
4: FeCl
3=5: 1: 0.1: 0.1 ratio preparation; 2, natural flake graphite is folded up in slide glass, and vertically be positioned in the two interior electrodes of reactive tank, keep graphite to have preferably and contact with reaction soln; 3, reactive tank is placed ultrasonator; 4, perfectly straight stream current stabilization electric current, holding current is 300 milliamperes; 5, by the adding of control reaction soln, the voltage of controlling two electrode pads is at 150 volts, and 6, ultrasonic concussion, at room temperature, reacted 3 minutes; 7, the graphite after handling is through washing, and dry down at 60 ℃; 8, dried expansible black lead is 920 ℃ pyroprocessing, the preparation expanded graphite.The expansion multiple of prepared expanded graphite is about 120 times, the content of no sulphur in the product.
Example 19: 1, preparation reaction soln, press diacetyl oxide: concentrated nitric acid: KMnO
4: FeCl
3=5: 1: 0.1: 0.1 ratio preparation; 2, natural flake graphite is folded up in slide glass, and vertically be positioned in the two interior electrodes of reactive tank, keep graphite to have preferably and contact with reaction soln; 3, reactive tank is placed ultrasonator; 4, perfectly straight stream current stabilization electric current, holding current is 300 milliamperes; 5, by the adding of control reaction soln, the voltage of controlling two electrode pads is at 50 volts, and 6, ultrasonic concussion, at room temperature, reacted 30 minutes; 7, the graphite after handling is through washing, and dry down at 30 ℃; 8, dried expansible black lead is 920 ℃ pyroprocessing, the preparation expanded graphite.The expansion multiple of prepared expanded graphite is about 180 times, the content of no sulphur in the product.
Example 20: 1, preparation reaction soln, press diacetyl oxide: concentrated nitric acid: KMnO
4: FeCl
3=5: 1: 0.1: 0.1 ratio preparation; 2, natural flake graphite is folded up in slide glass, and vertically be positioned in the two interior electrodes of reactive tank, keep graphite to have preferably and contact with reaction soln; 3, reactive tank is placed ultrasonator; 4, perfectly straight stream current stabilization electric current, holding current is 300 milliamperes; 5, by the adding of control reaction soln, the voltage of controlling two electrode pads is at 50 volts, and 6, ultrasonic concussion, at room temperature, reacted 30 minutes; 7, the graphite after handling is through washing, and dry down at 120 ℃; 8, dried expansible black lead is 920 ℃ pyroprocessing, the preparation expanded graphite.The expansion multiple of prepared expanded graphite is about 161 times, the content of no sulphur in the product.
Example 21: 1, preparation reaction soln, press diacetyl oxide: concentrated nitric acid: KMnO
4: FeCl
3=5: 1: 0.1: 0.1 ratio preparation; 2, natural flake graphite is folded up in slide glass, and vertically be positioned in the two interior electrodes of reactive tank, keep graphite to have preferably and contact with reaction soln; 3, reactive tank is placed ultrasonator; 4, perfectly straight stream current stabilization electric current, holding current is 300 milliamperes; 5, by the adding of control reaction soln, the voltage of controlling two electrode pads is at 50 volts, and 6, ultrasonic concussion, at room temperature, reacted 30 minutes; 7, the graphite after handling is through washing, and dry down at 60 ℃; 8, dried expansible black lead is 920 ℃ pyroprocessing, the preparation expanded graphite.The expansion multiple of prepared expanded graphite is about 161 times, the content of no sulphur in the product.
Example 22: 1, preparation reaction soln, press diacetyl oxide: concentrated nitric acid: KMnO
4: FeCl
3=5: 1: 0.1: 0.1 ratio preparation; 2, natural flake graphite is folded up in slide glass, and vertically be positioned in the two interior electrodes of reactive tank, keep graphite to have preferably and contact with reaction soln; 3, reactive tank is placed ultrasonator; 4, perfectly straight stream current stabilization electric current, holding current is 300 milliamperes; 5, by the adding of control reaction soln, the voltage of controlling two electrode pads is at 50 volts, and 6, ultrasonic concussion, at room temperature, reacted 30 minutes; 7, the graphite after handling is through washing, and dry down at 60 ℃; 8, dried expansible black lead is 600 ℃ pyroprocessing, the preparation expanded graphite.The expansion multiple of prepared expanded graphite is about 80 times, the content of no sulphur in the product.
Example 23: 1, preparation reaction soln, press diacetyl oxide: concentrated nitric acid: KMnO
4: FeCl
3=5: 1: 0.1: 0.1 ratio preparation; 2, natural flake graphite is folded up in slide glass, and vertically be positioned in the two interior electrodes of reactive tank, keep graphite to have preferably and contact with reaction soln; 3, reactive tank is placed ultrasonator; 4, perfectly straight stream current stabilization electric current, holding current is 300 milliamperes; 5, by the adding of control reaction soln, the voltage of controlling two electrode pads is at 50 volts, and 6, ultrasonic concussion, at room temperature, reacted 30 minutes; 7, the graphite after handling is through washing, and dry down at 60 ℃; 8, dried expansible black lead is 1100 ℃ pyroprocessing, the preparation expanded graphite.The expansion multiple of prepared expanded graphite is about 201 times, the content of no sulphur in the product.
Example 24: 1, preparation reaction soln, press diacetyl oxide: concentrated nitric acid: KMnO
4: FeCl
3=5: 1: 0.1: 0.1 ratio preparation; 2, natural flake graphite is folded up in slide glass, and make that the lamella direction of crystalline flake graphite and battery lead plate normal direction maintenance angle are 15 °, keep graphite to have preferably and contact with reaction soln; 3, reactive tank is placed ultrasonator; 4, perfectly straight stream current stabilization electric current, holding current is 300 milliamperes; 5, by the adding of control reaction soln, the voltage of controlling two electrode pads is at 50 volts, and 6, ultrasonic concussion, at room temperature, reacted 30 minutes; 7, the graphite after handling is through washing, and dry down at 60 ℃; 8, dried expansible black lead is 1100 ℃ pyroprocessing, the preparation expanded graphite.The expansion that prepared expanded graphite is 20～30 times, the content of no sulphur in the product.
Organic acid also can adopt acetate or propionic acid except that diacetyl oxide.
Method of the present invention under the effect of electric field force, utilizes the mode of electrophoresis to crystalline flake graphite Carry out oxidation processes. And polarization phenomena can not occur, and the expansible graphite quality that is prepared into Good, can prepare the expansible graphite that no sulphur hangs down nitrogen. The present invention is than the superiority of prior art: In the existing technology of preparing, because some defectives that self exist, although also can prepare high power The expanded graphite produsts of number, but its sulfur content is relatively high. This method combines traditional handicraft With the advantage of electrochemical method, adopt electrophoresis intercalation technology to prepare expansible graphite, avoided The high sulfur content of conventional method, and mainly utilize organic acid to be reaction medium. To the full extent Reduce the remnants of harmful components in the product, and kept good expansion multiple; And electrophoresis side Method can be accomplished quick preparation, and technology is simple and convenient.
Claims (8)
1. Preparation of Expansible Graphite method, may further comprise the steps: (1) is placed on crystalline flake graphite between the battery lead plate parallel in the reactive tank, graphite is soaked in the reaction solution, and makes itself and reaction solution keep well contacting; (2) add galvanic current between two electrodes, holding current is 100 to 600 milliamperes; (3) impedance of control reaction solution keeps between two electrodes voltage 50 to 250V; (4) graphite after the oxidation takes out washing, carries out drying under 30～120 ℃, makes expansible black lead.
2. Preparation of Expansible Graphite method according to claim 1 is characterized in that: the angle between the lamella direction of described crystalline flake graphite and the normal direction of battery lead plate is not more than 15 °.
3. Preparation of Expansible Graphite method according to claim 2 is characterized in that: the lamella direction of described crystalline flake graphite is consistent with battery lead plate planar normal direction.
4. Preparation of Expansible Graphite method according to claim 3 is characterized in that: described reaction solution is the mixing solutions of organic acid and nitric acid.
5. Preparation of Expansible Graphite method according to claim 4 is characterized in that: described organic acid can adopt diacetyl oxide, acetate or propionic acid.
6. Preparation of Expansible Graphite method according to claim 5 is characterized in that: described organic acid and nitric acid mixing solutions are organic acid, concentrated nitric acid, KMnO
4And FeCl
3Mixed solution, its mass ratio is an organic acid: concentrated nitric acid: KMnO
4: FeCl
3=8～5: 1: 0.1: 0.1.
7. Preparation of Expansible Graphite method according to claim 6 is characterized in that: described reactive tank places ultrasonator, and ultrasonic concussion is 3 to 30 minutes under the condition that keeps voltage between two electrodes.
8. Preparation of Expansible Graphite method according to claim 7 is characterized in that: described dried expansible black lead can make expanded graphite 600 to 1100 ℃ of pyroprocessing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100279209A CN1297475C (en) | 2004-06-30 | 2004-06-30 | Process for preparing expanded graphite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100279209A CN1297475C (en) | 2004-06-30 | 2004-06-30 | Process for preparing expanded graphite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1594076A true CN1594076A (en) | 2005-03-16 |
| CN1297475C CN1297475C (en) | 2007-01-31 |
Family
ID=34664077
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100279209A Expired - Fee Related CN1297475C (en) | 2004-06-30 | 2004-06-30 | Process for preparing expanded graphite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1297475C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106450312A (en) * | 2016-10-18 | 2017-02-22 | 福建翔丰华新能源材料有限公司 | Method for preparing inorganic doped modified natural graphite |
| CN109873116A (en) * | 2019-02-28 | 2019-06-11 | 华南理工大学 | A kind of worm graphite and preparation method thereof |
| CN111453723A (en) * | 2020-05-28 | 2020-07-28 | 鹰领航空高端装备技术秦皇岛有限公司 | Expandable graphite preparation device and electrochemical intercalation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1030535C (en) * | 1991-12-26 | 1995-12-20 | 清华大学 | Process and equipments for production of expandable graphite |
| CN1024819C (en) * | 1992-07-09 | 1994-06-01 | 清华大学 | Preparation for expansible graphite |
| CN1113215A (en) * | 1995-04-21 | 1995-12-13 | 清华大学 | Method for making expansible graphite with low-corrosivity |
-
2004
- 2004-06-30 CN CNB2004100279209A patent/CN1297475C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106450312A (en) * | 2016-10-18 | 2017-02-22 | 福建翔丰华新能源材料有限公司 | Method for preparing inorganic doped modified natural graphite |
| CN106450312B (en) * | 2016-10-18 | 2019-05-14 | 福建翔丰华新能源材料有限公司 | A kind of preparation method of inorganic doping modified natural graphite |
| CN109873116A (en) * | 2019-02-28 | 2019-06-11 | 华南理工大学 | A kind of worm graphite and preparation method thereof |
| CN109873116B (en) * | 2019-02-28 | 2022-04-22 | 华南理工大学 | Worm graphite and preparation method thereof |
| CN111453723A (en) * | 2020-05-28 | 2020-07-28 | 鹰领航空高端装备技术秦皇岛有限公司 | Expandable graphite preparation device and electrochemical intercalation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1297475C (en) | 2007-01-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10508037B2 (en) | Method for continuously preparing graphene oxide nanoplatelet | |
| Petersson et al. | Parameters influencing the ratio between electrochemically formed α-and β-PbO2 | |
| Li et al. | A Bio‐Inspired Trehalose Additive for Reversible Zinc Anodes with Improved Stability and Kinetics | |
| CN107634224B (en) | Preparation method of fluorinated multi-walled carbon nanotube containing outer wall of iron fluoride intercalation substance | |
| CN110316729B (en) | Method for preparing graphene based on high-concentration organic salt aqueous solution electrochemical intercalation | |
| CN102185140A (en) | Preparation method of nano-network conductive polymer coated lithium iron phosphate anode material | |
| Miao et al. | Dendrite‐Free Engineering toward Efficient Zinc Storage: Recent Progress and Future Perspectives | |
| CN106129390B (en) | A kind of lithium-sulphur cell positive electrode graded porous carbon/sulphur composite material and preparation method | |
| CN107195906A (en) | A kind of porous carbon cloth, preparation method and applications | |
| CN111509247B (en) | Method for regenerating electrolyte of failure vanadium battery | |
| CN114604864A (en) | Method for preparing graphene by stripping graphite material by virtue of confined electrochemical method | |
| Bi et al. | A study on the effect of introducing S-doped GO into the active layer on the performance of wire mesh Ti/Ce-Mn/SnO2-Sb-La electrodes | |
| Huang et al. | Proton/Mg2+ Co‐Insertion Chemistry in Aqueous Mg‐Ion Batteries: From the Interface to the Inner | |
| CN114852998A (en) | Method for preparing polyaniline hybridized graphene material by electrochemical intercalation method | |
| CN103014800B (en) | The preparation method of the graphite-based plumbic oxide catalysis electrode of cerium dopping | |
| CN1297475C (en) | Process for preparing expanded graphite | |
| Wang et al. | Oxygen vacancy defect engineering of porous single-crystal VO2 nanobelts for aqueous zinc ion battery cathodes | |
| CN110164712B (en) | Lithium ion capacitor electrode material and preparation method thereof | |
| CN112713280A (en) | Preparation method of noble metal platinum-based redox catalyst carrier | |
| CN1030535C (en) | Process and equipments for production of expandable graphite | |
| CN105854858B (en) | A kind of method for carrying out electrochemical desorption inorganic anion by improving cathode potential | |
| CN114195137A (en) | Method for preparing graphene | |
| Tasaka et al. | Effect of Trace Elements on the Electrolytic Production of NF 3 | |
| CN106992294A (en) | High-voltage lithium nickel manganate anode composite material and preparation method thereof, lithium ion battery | |
| CN114335447A (en) | Surface treatment method for improving zinc negative polarity performance and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070131 Termination date: 20120630 |