CN105977458B - Nano-diamond powder and the combination electrode material of graphene and preparation method thereof - Google Patents
Nano-diamond powder and the combination electrode material of graphene and preparation method thereof Download PDFInfo
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Abstract
本发明公开一种用于锂电池负极的纳米金刚石粉/石墨烯复合电极材料及其制备方法。本方法具体是以柠檬酸、尿素、纳米金刚石粉作为碳源，经微波加热处理，得到块状固体粉末，之后在惰性气体保护下进行高温碳化处理，获得复合电极材料；也可以将纳米金刚石粉与石墨烯直接进行混合，在无水乙醇中高频超声处理、再干燥获得复合电极材料。纳米金刚石粉/石墨烯复合电极材料研磨成粉末，与其他碳材料在粘结剂的作用下充分研磨混合，制得锂离子电池的负电极。本方法的纳米金刚石粉/石墨烯复合电极材料作为阴极制成的锂离子电池具有比容量高、循环性能好、充放电库伦效率大等优良的性能。而且制备方法简单、成本低、绿色环保，具有良好的应用前景。
The invention discloses a nano-diamond powder/graphene composite electrode material for a negative electrode of a lithium battery and a preparation method thereof. In this method, citric acid, urea, and nano-diamond powder are used as carbon sources, and after microwave heating treatment, massive solid powder is obtained, and then high-temperature carbonization treatment is performed under the protection of inert gas to obtain composite electrode material; It is directly mixed with graphene, subjected to high-frequency ultrasonic treatment in absolute ethanol, and then dried to obtain a composite electrode material. The nano-diamond powder/graphene composite electrode material is ground into powder, and fully ground and mixed with other carbon materials under the action of a binder to prepare a negative electrode for a lithium ion battery. The lithium ion battery made of the nano-diamond powder/graphene composite electrode material as a cathode has the excellent properties of high specific capacity, good cycle performance, high charge-discharge Coulomb efficiency and the like. Moreover, the preparation method is simple, low in cost, green and environmentally friendly, and has a good application prospect.
Description
Technical field
The invention belongs to the technical field of lithium ion battery negative material, it is related to a kind of nano-diamond powder and graphene
Combination electrode material and preparation method thereof.
Background technique
Secondary cell is hyundai electronics electric appliance such as mobile phone, laptop computer, electric tool, electric vehicle, national defence and aviation
The core component of electronic apparatus, lithium ion battery is with its high-energy density, long circulation life, memory-less effect, environmental-friendly etc.
Advantage becomes the first choice in secondary cell, and exploitation high performance lithium ion battery will greatly alleviate energy shortage, improve environment, right
Developing national economy and safeguarding national security is of great significance.Whether the energy density and circulation of lithium ion battery are able to ascend
Performance and the key factor in service life first is that the negative electrode material of lithium ion battery.Currently, commercialized negative electrode of lithium ion battery material
Expect mainly based on graphitic carbon material, however its theoretical embedding lithium capacity 372mAhg-1It is too low, it is not able to satisfy product demand, Ren Menyi
There is the negative electrode material of excellent performance to replace graphitic carbon material for straight research and development.Silicon has due to its theoretical specific capacity highest, reachable
To 4200mAhg-1, at room temperature, actual specific capacity is up to 3579mAhg-1, it is concerned by people, but silicon electric conductivity is poor, it is special
It is easy to happen huge volume expansion when being not removal lithium embedded, will seriously affect the cycle performance of electrode material.In recent years, research hair
Existing SnO, SnO2Equal Sn-polymetallic orefields, FeO, CoO, MoO and Cu2The transition metal oxides such as O, specific discharge capacity are greater than
600mAhg-1, but during battery charging and discharging reaction, volume changes also very greatly, causes the failure of electrode material
Even dusting, leads to that its actual capacity is lower and cyclical stability is not high, and with the progress of charge and discharge cycles, capacity attenuation is very
Fastly.Therefore a kind of and mature technology compatibility, and simple process, low cost, and the high, cyclical stability with specific capacity are provided
The negative electrode material of the excellent chemical properties such as good, good rate capability is necessary.
Application No. is a kind of 201510104614.9 entitled " preparations of big size graphene/composite cathode material of silicon/carbon/graphite
The preparation method of the patent application of method ", disclosed graphene/composite cathode material of silicon/carbon/graphite is to be added to sulphur using crystalline flake graphite
The mixed acid process of acid and nitric acid prepares graphite oxide, and potassium permanganate and H is added2O2Large scale graphene oxide is further prepared,
Then the sonicated mixture solution for obtaining large scale graphene oxide and graphite, then it is annealed, obtain large scale graphite
Alkene composite cathode material of silicon/carbon/graphite.Big size graphene/composite cathode material of silicon/carbon/graphite lithium storage content of this method preparation is
372mAhg-1~401mAhg-1, coulombic efficiency is 85%~90%, and capacity attenuation is 162mAhg under 5C multiplying power-1, cyclicity
Can be poor, and preparation process is more complex, and generates biggish environmental pollution.
The close prior art is the patent application application No. is 201510545536.6, a kind of " doping stone with the present invention
The porous carbon of black alkene/ferriferrous oxide nano fiber lithium cell cathode material and preparation method thereof ", it is to utilize electrostatic spinning skill
Polyacrylonitrile/polymethyl methacrylate nano fiber of art preparation doping molysite and graphene, passes through pre-oxidation and pyrocarbon
Change obtains porous carbon/ferriferrous oxide nano fiber lithium cell cathode material of doped graphene.The doping of this method preparation
The porous carbon of graphene/ferriferrous oxide nano fiber lithium cell cathode material lithium storage content is 720 mAhg-1~
754mAhg-1, capacity attenuation is 480mAhg under 5C multiplying power-1, cycle performance is poor, and Fe3O4It can be sent out during embedding de- lithium
Raw huge volume change and serious particle aggregation, cause charge and transmission and diffusion poor, as negative electrode material meeting
Make that the cyclical stability of battery is poor, high rate performance is not high.
Nano diamond is important a kind of carbon material, and not only hardness is high, intensity is big, chemical stability is good, thermal conductivity is excellent
It is good, and large specific surface area, high surface activity, composite deposite, precise polished, mechanical lubrication, drug loading, magnetic recording,
Extensive application in the numerous areas such as electronic imaging.Explosion method Nano diamond can be used in Nano diamond, generallys use stone
Prepared by detonation under the conditions of negative oxygen of black micro mist and explosive composition.The absorption of lithium can be increased using Nano diamond, improved
Reversible capacity and lithium ion transport rate.Diamond nano-particles have the advantages that stable, volume change is small.By Nano diamond
It is made into composite construction with other carbon nanomaterials to be introduced into lithium cell cathode, it will improve the performance of cathode and battery.
Summary of the invention
The technical problem to be solved by the present invention is to, will be traditional by the selection of functional material and the design of special construction
Graphene material and diamond nano material combine, and obtain a kind of one kind that chemical property is good, at low cost, environmentally protective
The electrode material of new construction.
The present invention prepares carbon material using microwave assisting method, by adding different quality ratio in the pre-reaction material of carbon
Nano-diamond powder obtains the combination electrode material of a kind of nano-diamond powder and graphene nanometer sheet, to further improve
The storage lithium performance of carbon material.
The specific technical solution of electrode material of the invention is as follows.
A kind of nano-diamond powder and graphene combination electrode material, characterized in that in the laminated structure of multilayer, surface is deposited
In corrugated fold, Nano diamond grain is adsorbed on graphene film surface；The mass ratio of nano-diamond powder and graphene is
0.066~0.334: 1.
The Nano diamond grain, particle size are 5~10nm.
Above-mentioned nano-diamond powder and graphene combination electrode material is prepared with two methods --- microwave assisting method
And direct mixing method.The preparation method specific technical solution difference of electrode material is as described below.
Microwave assisting method prepares nano-diamond powder and the technical solution of graphene combination electrode material is: a kind of nanogold
Citric acid and urea are dissolved in appropriate amount of deionized water and form nothing by the preparation method of emery and graphene combination electrode material
Color clear solution, then adds nano-diamond powder, handles 30~60min through high frequency ultrasound, acquired solution is placed in micro-wave oven
In 10~15min is heated under 850W power, solution eventually becomes dark-brown solid composite by the colourless yellowish-brown that becomes；It will
Obtained solid composite is through drying again 900 DEG C carbonization treatment 2 hours under inert gas protection, obtained nano-diamond powder
And graphene combination electrode material.
Wherein, the mass ratio of citric acid and urea can be 1: 3~4；The quality and citric acid and urine of nano-diamond powder
The ratio of plain quality sum is 0.005~0.025: 1.
The solid composite can dry 1~2h, under the conditions of 60~80 DEG C through drying to remove remaining water
Point.
Direct mixing method prepares nano-diamond powder and the technical solution of graphene combination electrode material is: a kind of nanogold
The preparation method of emery and graphene combination electrode material carries out nano-diamond powder and graphene in mass ratio 1: 3~4
Mixing, handles 6-8h through high frequency ultrasound in dehydrated alcohol；Then by the suspension of graphene and nano-diamond powder at 60 DEG C
Under the conditions of dry to dehydrated alcohol evaporating completely, obtain nano-diamond powder/graphene combination electrode material.
Use the negative electrode of nano-diamond powder and graphene combination electrode material production lithium ion battery, detailed process
It is: nano-diamond powder and graphene combination electrode material is pulverized and grinds until powder granule size reaches nanoscale, with
Carbon black (the helping conductive agent) mixing that lithium cell cathode uses, grinds under the action of polyvinylidene fluoride (PVDF, binder), and
A certain amount of 1-Methyl-2-Pyrrolidone (NMP, solvent) is added so that using magnetic stirrer at viscous fluid；It will be sticky
Fluid is applied to collector, dry at 120 DEG C；It is finally cut into electrode shape compacting, nano-diamond powder is made and graphene is multiple
The negative electrode of the lithium ion battery of conjunction.
Wherein, nano-diamond powder/graphene combination electrode material in mass ratio: Kynoar: carbon black is 8: 1: 1；
The collector is copper foil；It is dry at described 120 DEG C, it is the dry 12h in 120 DEG C of vacuum ovens.
The present invention further provides a kind of lithium ion half-cells: anode is pair with metal lithium sheet in the environment of anhydrous and oxygen-free
Electrode, nano-diamond powder/graphene composite material that cathode is prepared containing the with good grounds above method.Experimental measurements table
Bright, resulting carbon composite is used as specific discharge capacity of the lithium ion battery negative material after first charge-discharge circulation and reaches
1085mAhg-1, first charge-discharge efficiency 60%, much higher than the theoretical circulation capacity 372mAhg of graphite-1.With cycle-index
Increase, discharge capacity has small size decline, and the charge/discharge capacity after 50 circulations has reached 650mAhg-1, capacity retention ratio
It is 59.9%, charge and discharge coulombic efficiency is close to 100%.
The present invention utilizes the compound acquisition novel composite electrode material of nano-diamond powder/graphene, and the two forms collaboration effect
It answers, prepares high performance novel pure carbon lithium ion cell negative electrode material, the specific capacity for solving commercial graphite cathode is low and novel
The problems such as high discharge platform of graphene cathode, low coulombic efficiency for the first time；Not only hardness is high, thermal conductivity is excellent for nano-diamond powder
It is good, and large specific surface area, stable structure can avoid the urgency of volume in charge and discharge process when as lithium cell cathode material
Drastic change and caused by capacity fade problem, and the big specific surface area of nano-diamond powder is beneficial to the storage of lithium ion, for
The specific capacity of negative electrode material is improved, the cyclical stability kept is most important.Nano-diamond powder and graphene of the invention
The preparation method of combination electrode material has process simple, low in cost, it is easy to accomplish, it is easy the advantages that amplifying, is expected to future
Large-scale production.
Detailed description of the invention
Fig. 1 is the transmission electron microscope picture of sample 1#.
Fig. 2 is the transmission electron microscope picture of sample 4#.
Fig. 3 is the comparison diagram of X-ray diffraction (XRD) material phase analysis of sample 1# and 4#.
Fig. 4 is the Raman spectrum comparison diagram of sample 1# and 4#.
Fig. 5 is that sample 1# and 4# are used for negative electrode of lithium ion battery charge/discharge capacity perseverance circulation performance comparison figure.
Fig. 6 is that sample 1# and 4# are used for negative electrode of lithium ion battery charge/discharge capacity zoom rate cycle performance comparison diagram.
Fig. 7 is sample 1# charge and discharge cycles volt-ampere test chart.
Fig. 8 is sample 1# perseverance rate charge-discharge curve test figure.
Fig. 9 is sample 4# charge and discharge cycles volt-ampere test chart.
Figure 10 is sample 4# perseverance rate charge-discharge curve test figure.
Figure 11 is the adsorption-desorption curve of sample 1# and 4#.
Figure 12 is the transmission electron microscope picture of sample 6#.
Specific embodiment
The application is described in further detail below in conjunction with attached drawing and embodiment, it should be pointed out that reality as described below
It applies example to be intended to convenient for the understanding to the application, and does not play any restriction effect to it.
Embodiment 1: nano-diamond powder/graphene nanometer sheet combination electrode material microwave assisting method preparation
2g citric acid and 6g urea are dissolved in 30ml deionized water (20~40ml) and form colourless transparent solution,
Then (additive amount of nano-diamond powder accounts for citric acid, urine to the bortz powder that addition 0.16g particle size is 5~10nm nanometers
The 1.9%~2.0% of element, nano-diamond powder mixture quality), 30~60min is handled through high frequency ultrasound, acquired solution is set
10min is heated under 850W power in micro-wave oven, solution eventually becomes dark-brown solid reaction by the colourless yellowish-brown that becomes
Terminate.Then obtained solid composite is moved into vacuum oven, dry 1h under the conditions of 60 DEG C is remaining in molecule to remove
Moisture.Solid composite after drying is pulverized and is ground to powdered, powder granule is less than 10 μm, to increase the ratio table of material
Area.It is put into tube furnace, carbonization treatment is carried out under inert gas argon gas shielded, 900 DEG C are calcined 2 hours.The carbon obtained at this time
Compound becomes black blocks of solid from original dark-brown, continues to pulverize and grind 3~4h, until powder granule size reaches
Nanoscale.Nano-diamond powder obtained/graphene combination electrode material sample is labeled as sample 4#.
As the nano-diamond powder 0.16g of raw material in the present embodiment, being prepared into, nano-diamond powder/graphene is compound
It is held essentially constant after electrode material, or slightly reduces.The finally obtained carbon complex that is carbonized is nano-diamond powder and stone
The mixture of black alkene weighed calculate for 0.76g the quality of graphene is about 0.6g, i.e. nano-diamond powder and graphene
Mass ratio is 0.26: 1.
The transmission electron microscope picture of sample 4# is shown in that Fig. 2, X-ray diffraction (XRD) spectrum are shown in that Fig. 3, Raman spectrum are shown in Fig. 4.With sample 4#
The negative electrode of lithium ion battery of production is used for lithium ion battery, and embodiment 4 is shown in performance test.
X-ray diffraction (XRD) material phase analysis of the present embodiment sample 4# carries out on the polycrystalline XRD instrument of XRD-6000, Cu
Target, K α radiation source (λ=0.15418nm).The XRD spectrum of Fig. 3 can see 2 more apparent peaks, be located at 2 θ=26 °
Near 44 °, (002) face and (101) face of six purpose square graphites have been corresponded to.Show that sample 4# has graphite-structure.Sample 4#'s spreads out
It penetrates that peak peak shape is sharp, and signal is also preferable, shows the good crystallinity of sample 4#.The Raman spectrum (Raman) of the present embodiment sample 4#
Analysis is copolymerized on burnt micro-Raman spectroscopy in Renishaw inVia type and carries out, light source Ar+Laser, wavelength 514.5nm.
Raman result as shown in figure 4, sample 4# in (800-2000) cm-1Between there are two apparent characteristic peaks, be respectively
1350cm-1The neighbouring peak D and 1580cm-1The neighbouring peak G.In 2650-3000cm-1There is second order Raman peaks (i.e. the peak 2D) on section.
JEM-2200FS Flied emission transmission electron microscope is used to the morphology analysis of the present embodiment sample 4#.The sample 4# that Fig. 2 is provided
Transmission electron microscope picture.Fig. 2 shows the graphene film surface for being adsorbed on fold of Nano diamond grain densification, a large amount of nanogold
Hard rock grain can improve the specific surface area (as shown in Figure 11 N2 adsorption BET specific surface area test curve) of sample, and Nano diamond
Particles benefit can be used as a kind of ideal lithium ion battery material in the storage density and transmission rate that improve lithium ion.
The preparation of embodiment 2 pure grapheme material (nano-diamond powder is not added) microwave assisting method
Pure graphite is prepared using the raw material proportioning (nano-diamond powder is not added) and technical process of embodiment 1 as comparative example
Alkene material.Particularly:
Citric acid 2g and urea 6g are dissolved in 30ml deionized water and form colourless transparent solution, is handled through high frequency ultrasound
Acquired solution is placed in micro-wave oven under 850W power and heats 10min by 30~60min, and solution becomes yellowish-brown most by colourless
After become dark-brown solid reaction and terminate.Then obtained solid product is moved into vacuum oven, drying under the conditions of 60 DEG C
1h.Solid product after drying is pulverized and is ground to powdered, powder granule is less than 10 μm.It is put into tube furnace, is protected in argon gas
Shield is lower to carry out carbonization treatment, and 900 DEG C are calcined 2 hours.Obtained carbonized solid product continues to pulverize and grind 3~4h, until powder
Body particle size reaches nanoscale.Pure grapheme material sample obtained is labeled as sample 1#.
Sample 1# is as a comparison sample to make comparisons with sample 4#, as a result as follows.
The XRD result of sample 1# as shown in figure 3, XRD spectrum it can also be seen that 2 more apparent peaks, are located at 2 θ
Near=26 ° and 44 °, (002) face and (101) face of six purpose square graphites have been corresponded to.Show that sample 1#, 4# all have graphite-structure.
In map, sample 4# is more sharp than the diffraction maximum peak shape of sample 1#, and signal is also slightly good, shows the crystallinity of sample 4# compared to sample
Product 1# is some higher, and the material of sample 4# has good layer structure, is more suitable for the insertion and abjection of lithium ion.Sample 1#'s
Raman spectrum (Raman) analyzes result as shown in figure 4, sample 1# is also in (800-2000) cm-1Between exist two it is obvious
Characteristic peak, be 1350cm respectively-1The neighbouring peak D and 1580cm-1The neighbouring peak G.In 2650-3000cm-1There is second order on section
Raman peaks (i.e. the peak 2D).The pattern of sample 1# is as shown in the transmission electron microscope picture of Fig. 1, and as seen from Figure 1, sample is multilayer
Laminated structure, there are a degree of folds, such as corrugated on surface.With sample 1# production negative electrode of lithium ion battery for lithium from
Embodiment 5 is shown in sub- battery, performance test.As can be seen that the negative electrode of lithium ion battery of sample 4# production is used in embodiment 5
The performance of lithium ion battery is more outstanding than sample 1# very much.
The preparation of 3 nano-diamond powders of embodiment/graphene nanometer sheet combination electrode material microwave assisting method
Addition 0.04g, 0.08g, 0.20g partial size ruler in 30ml deionized water is dissolved in 2g citric acid and 6g urea respectively
Very little is 5~10nm nanometers of bortz powder, and (additive amount of nano-diamond powder accounts for citric acid, urea, nano-diamond powder mixing
Amount of substance 0.5%, 1.0%, 2.5%), through similarly to Example 1 high frequency ultrasound processing, microwave stove heating, vacuum drying
Case is dry, pulverizes grinding, carbonization treatment is carried out under inert gas argon gas shielded, continues to pulverize and grind, nanogold obtained
Emery/graphene combination electrode material sample is labeled as sample 2#, sample 3#, sample 5#.
It is about 0.6g to sample 2#, sample 3#, sample the 5# quality for obtaining graphene through weighing and calculating, reaction front and back nanogold
The mass conservation of emery learns that sample 2#, sample 3#, the mass ratio of nano-diamond powder and graphene is respectively in sample 5#
0.066∶1、0.13∶1、0.33∶1。
Sample 2#, sample 3#, sample 5# can be used as the negative electrode material of lithium ion battery.
4 nano-diamond powder of embodiment is prepared with the electrode material that graphene directly mixes
Present embodiments provide to the present invention another prepare Nano diamond/Graphene electrodes method.It will directly receive
Rice bortz powder is mixed with graphene in mass ratio 1: 3~4, is handled 6-8h through high frequency ultrasound in dehydrated alcohol, is made two
Person mixes more abundant.Then the suspension of graphene and nano-diamond powder is moved into vacuum oven, under the conditions of 60 DEG C
Drying is until dehydrated alcohol evaporating completely.Finally the solid mixture after drying is pulverized and is fully ground to powdered.It obtains
Nano-diamond powder/graphene combination electrode material be denoted as sample 6#.
Figure 12 is sample 6# transmission electron microscope picture made from the graphene of commercialization and the mixing of nano-diamond powder, from figure
In it can be seen that Nano diamond grain dispersion on graphene film surface, forms nano-diamond powder/graphene combination electrode material
Material, obtains and result similar in Examples 1 and 2.
Nano-diamond powder/graphene nanometer sheet composite material production lithium ion battery the cathode of embodiment 5
Negative electrode of lithium ion battery is using 80wt% Nano diamond/graphene composite material (active material), 10wt%
Binder (Kynoar, PVDF) and 10wt%'s helps the mixing of conductive agent carbon black to constitute.It is packed into after three's mixed grinding 0.5h
In container, a certain amount of 1-Methyl-2-Pyrrolidone (NMP, solvent) of addition is placed on magnetic stirring apparatus at the uniform velocity again in container
6h is stirred, so that mixture is viscous fluid.Using copper foil as collector, above-mentioned mixing dope is applied on copper foil, coating
Density needs uniform.By the temperature setting of vacuum oven at 120 DEG C, and above-mentioned copper foil smear is taken to put in a drying box, timing 12h
Afterwards, it takes out stand-by.The copper foil smear special cutter mold that will be prepared, is cut into several electrode disks, after with tablet press machine pressure
Active material on real pole piece, comes into full contact with it with collector, prevents de- material.
Embodiment 6: the production and performance test of lithium ion battery
Using sample 1#, 4# as Typical Representative, its performance for being used for lithium ion battery is tested.With the sample of pure graphene nanometer sheet
Product 1# is contrast sample.The lithium ion battery of test preparation is CR-2025 type button cell.Negative electrode material is living using 80wt%
Property substance, the binder (Kynoar, PVDF) of 10wt% and 10wt% the conductive agent carbon black mixing that helps constitute, made with copper foil
For collector.The copper foil smear special cutter mold that will be prepared, is cut into several electrode disks, after with tablet press machine be compacted electricity
Active material on pole piece, comes into full contact with it with collector.Then electrode tablet quality is weighed, in case the specific capacity of calculated for subsequent
Parameter etc..Matched battery plus-negative plate shell, gasket, elastic slice and polypropylene diaphragm are taken, electrolyte, electrode slice etc. is according to lithium electricity
The production predetermined operation in pond, the safe and orderly operation in glove box encapsulate battery.Using sample 1#, 4# as cathode of lithium battery activity
Battery obtained by material is respectively labeled as S1, S2.
1) charge-discharge magnification is tested
Battery S1, the S2 prepared in testing example 3 in blue electrical measurement test system.At 25 DEG C, according to certain electric discharge
Current discharge is to 0.02V；After electric discharge, battery standing 3 minutes；Then it is filled with certain current density constant-current charge to 3V
After electricity, with identical current density constant-current discharge to 0.02V after battery standing 3 minutes；Battery stands 3 minutes after completely filling,
Again with the charging of identical condition.Electrochemical property test result is as shown in figure 5, the as can be seen from the figure electric discharge for the first time of sample 4#
1085mAhg has been respectively reached with charge specific capacity-1And 749mAhg-1, discharging efficiency is 61% for the first time, with cycle-index
Increase, discharge capacity has small size decline, and the charge/discharge capacity of the 50th circulation is 646mAhg-1, close to graphite theoretical capacity
2 times, charge and discharge coulombic efficiency is close to 100%.The circulation volume for the first time of sample 1# is respectively 874.7mAhg-1And 444.2mAhg-1, discharging efficiency is 51% for the first time, and capacity is maintained at 300mAhg after stable circulation-1Near, coulombic efficiency is also close to 100%.This
One capacity is lower than the capacity of sample 4#.
Become multiplying power discharging, is successively set as 0.2C, 0.5C, 1C, 5C, 10C, the reversible specific volume that charges is carried out to battery S1, S2
Measure examination.Electrochemical property test result is as shown in Figure 6.As seen from the figure, nano-diamond powder/graphene nanometer sheet is compound
Battery S2 made from material (sample 4#) becomes under rate charge-discharge situation, has good specific capacity and conservation rate, it is shown that excellent
Different chemical property.
2) charge and discharge cycles volt-ampere is tested
Cyclic voltammetry condition is that test temperature is controlled at 25 DEG C, and Applied Electrochemistry work station, scanning speed, which is arranged, is
0.1mV/s, selecting sample 1#, 4# is electrode active material.Cyclic voltammetric as preceding 5 circulations are set forth in Fig. 7,8 is bent
Line, it can be seen that other than having special peak to occur in first time circulation, after second of circulation, CV curve tends towards stability.
As can be seen from the figure the stability of sample 4# is more preferable compared with sample 1#.In first time cyclic curve, it is located at 0.3V to 1.0V and locates
Wide characteristic peak has corresponded to the generation of solid electrolyte interface film (SEI).SEI film is in lithium ion battery first charge-discharge process
In, electrode material and electrolyte react on solid-liquid phase interface and form one layer of passivation for being covered in electrode material surface
Layer, which can prevent the further reaction of electrolyte, to improve the stability of battery.There is the electrode shape of Nano diamond
At more stable SEI film, help to obtain the battery of good characteristic
3) permanent rate charge-discharge curve test
The permanent rate charge-discharge curve of battery S1, S2 for being prepared using sample 1#, 4# as electrode active material respectively as Fig. 9,
Shown in 10, multiplying power size is 0.2C, voltage range 0.02-3V, gives representational 5 curves in figure.For the first time
In charging and discharging curve, it can be seen that have an obvious discharge platform near 0.6V, corresponded to the peak SEI of CV curve.
Charge/discharge capacity tends towards stability in subsequent circulation.This shows that the irreversible loss of capacity occurs mainly in first time charge and discharge
In the process.The circulation volume for the first time of sample 1# is respectively 874.7 and 444.2mAhg as shown in Figure 9-1, for the first time discharging efficiency be
51%, 10 it can be seen that the electric discharge for the first time of sample 4# and charge specific capacity have respectively reached 1085 and 749mAhg from figure-1, far
Higher than the theoretical capacity 372mAhg of graphite-1, irreversible capacity 336mAhg-1, discharging efficiency is 61% for the first time, is higher than sample
1#.Charging and discharging curve is almost unchanged, shows there is preferable cyclical stability.In conclusion nano-diamond powder/graphene
Battery S2 made from nanosheet composite material (sample 4#) has good specific capacity compared with battery S1 made from (sample 1#) and protects
Holdup, it is shown that excellent chemical property.
Claims (7)
1. a kind of nano-diamond powder and graphene combination electrode material, characterized in that in the laminated structure of multilayer, surface exists
Corrugated fold, Nano diamond grain are adsorbed on graphene film surface；The mass ratio of nano-diamond powder and graphene is 0.066
~0.334: 1.
2. nano-diamond powder according to claim 1 and graphene combination electrode material, characterized in that the nanometer
Diamond grain, particle size are 5~10nm.
3. a kind of nano-diamond powder of claim 1 and the preparation method of graphene combination electrode material, by citric acid and urine
Element, which is dissolved in appropriate amount of deionized water, forms colourless transparent solution, then adds nano-diamond powder, through high frequency ultrasound processing 30
Acquired solution is placed in micro-wave oven 10~15min of heating, solution under 850W power and becomes yellowish-brown by colourless by~60min
Eventually become dark-brown solid composite；By obtained solid composite through drying again 900 DEG C of carbon under inert gas protection
Change processing 2 hours, obtained nano-diamond powder and graphene combination electrode material.
4. the preparation method of nano-diamond powder according to claim 3 and graphene combination electrode material, characterized in that
The mass ratio of citric acid and urea is 1: 3~4；The ratio of the sum of the quality and citric acid of nano-diamond powder and urea quality is
0.005~0.025: 1.
5. a kind of nano-diamond powder of claim 1 and the preparation method of graphene combination electrode material, by Nano diamond
Powder is mixed with graphene in mass ratio 1: 3~4, handles 6~8h through high frequency ultrasound in dehydrated alcohol；Then by graphene
It is dried under the conditions of 60 DEG C to dehydrated alcohol evaporating completely with the suspension of nano-diamond powder, obtains nano-diamond powder/stone
Black alkene combination electrode material.
6. a kind of nano-diamond powder of claim 1 and the purposes of graphene combination electrode material, for making lithium-ion electric
The negative electrode in pond；Detailed process is: nano-diamond powder and graphene combination electrode material being pulverized and ground until powder
Particle size reaches nanoscale, mixes with carbon black, grinds under the action of polyvinylidene fluoride, and adds 1- methyl -2- pyrrolidines
Ketone is down to use magnetic stirrer at viscous fluid；Viscous fluid is applied to collector, it is dry at 120 DEG C；Finally it is cut into
Electrode shape compacting, is made the negative electrode of nano-diamond powder and the compound lithium ion battery of graphene.
7. the purposes of nano-diamond powder according to claim 6 and graphene combination electrode material, characterized in that press matter
Amount is than nano-diamond powder/graphene combination electrode material: Kynoar: carbon black is 8: 1: 1；The collector is copper
Foil；It is dry at described 120 DEG C, it is the dry 12h in 120 DEG C of vacuum ovens.
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| CN106683900A (en) * | 2017-02-27 | 2017-05-17 | 安徽桑瑞斯环保新材料有限公司 | Supercapacitor battery |
| CN107689463A (en) * | 2017-07-21 | 2018-02-13 | 昆山正国新能源动力电池有限公司 | Lithium battery multi-layer graphene and preparation method thereof |
| CN107482252A (en) * | 2017-07-21 | 2017-12-15 | 昆山正国新能源动力电池有限公司 | Electrolyte for lithium ion battery and preparation method |
| CN107546414A (en) * | 2017-07-21 | 2018-01-05 | 昆山正国新能源动力电池有限公司 | Low temperature lithium battery electrolytes and preparation method thereof |
| CN107482251A (en) * | 2017-07-21 | 2017-12-15 | 昆山正国新能源动力电池有限公司 | High Temperature Lithium Cell electrolyte and preparation method thereof |
| CN107591518A (en) * | 2017-08-04 | 2018-01-16 | 郴州国盛新材科技有限公司 | A kind of fastening lithium ionic cell and its preparation method and application |
| CN108217631A (en) * | 2018-01-25 | 2018-06-29 | 中国工程物理研究院化工材料研究所 | A kind of preparation method of the graphene/nanometer diamond laminated film of fold enrichment |
| GB2585621B (en) * | 2018-09-24 | 2022-11-16 | Plasma App Ltd | Carbon materials |
| CN110071276A (en) * | 2019-04-26 | 2019-07-30 | 吉林大学 | Nano diamond and SiOxCombination electrode material and preparation method |
| CN113371688A (en) * | 2021-06-07 | 2021-09-10 | 南阳师范学院 | Preparation method of novel iron nitride and porous carbon composite anode material |
| CN113713806B (en) * | 2021-08-30 | 2022-05-20 | 广东工业大学 | Preparation method of nanodiamond/graphene supported Pt single-atom catalyst |
| CN114142161B (en) * | 2021-11-26 | 2023-09-22 | 吉林大学 | A kind of preparation method of modified lithium-ion battery separator |
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