CN105977458A - Nano diamond powder and graphene composite electrode material and preparation method thereof - Google Patents
Nano diamond powder and graphene composite electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a nano diamond powder/graphene composite electrode material for a negative electrode of a lithium battery and a preparation method of the nano diamond powder/graphene composite electrode material. The method specifically comprises the steps as follows: heating treatment is carried out on a citric acid, urea and nano diamond powder as a carbon source via a microwave manner to obtain blocky solid powder and then high-temperature carbonization treatment is carried out under inert gas protection to obtain the composite electrode material; the nano diamond powder can also be directly mixed with graphene, and the mixture is subjected to high-frequency ultrasonic treatment in absolute ethyl alcohol and is dried to obtain the composite electrode material; and the nano diamond powder/graphene composite electrode material is ground into powder, and the powder and other carbon materials are fully ground and mixed under the action of a binder to prepare the negative electrode of the lithium-ion battery. The lithium-ion battery prepared from the nano diamond powder/graphene composite electrode material prepared by the method as the negative electrode has excellent properties of high specific capacity, good cycle performance, high charge-discharge coulomb efficiency and the like; the preparation method is simple; the cost is low; and the nano diamond powder/graphene composite electrode material is green and environment-friendly and has a good application prospect.
Description
Technical field
The invention belongs to the technical field of lithium ion battery negative material, relate to combination electrode material of a kind of nano-diamond powder and Graphene and preparation method thereof.
Background technology
Secondary cell is hyundai electronics electrical equipment such as mobile phone, laptop computer, electric tool, electric motor car, national defence and the core component of aviation electronics electrical equipment, lithium ion battery is with its high-energy-density, long circulation life, memory-less effect, advantages of environment protection, become the first-selection in secondary cell, exploitation high performance lithium ion battery will greatly alleviate energy shortage, improve environment, developing national economy is significant with safeguarding national security.One of energy density and the key factor in cycle performance and life-span that whether can promote lithium ion battery are the negative materials of lithium ion battery.At present, business-like lithium ion battery negative material is mainly based on graphitic carbon material, but its theoretical embedding lithium capacity 372mAhg-1The lowest, it is impossible to meet product demand, people research and develop the negative material of the performance with excellence always and replace graphitic carbon material.Silicon has owing to its theoretical specific capacity is the highest, can reach 4200mAhg-1, under room temperature, actual specific capacity is up to 3579mAhg-1, paid close attention to by people, but silicon electric conductivity be poor, particularly during removal lithium embedded, be susceptible to huge volumetric expansion, the cycle performance of electrode material will be had a strong impact on.In recent years, research finds SnO, SnO2Deng Sn-polymetallic orefield, FeO, CoO, MoO and Cu2The transition metal oxides such as O, specific discharge capacity is more than 600mAhg-1But, during battery charging and discharging reacts, volume changes the biggest, causes the inefficacy even efflorescence of electrode material, causes its actual capacity relatively low and cyclical stability is the highest, and along with the carrying out of charge and discharge cycles, its capacity attenuation is quickly.Therefore provide a kind of and maturation process compatibility, and technique is simple, low cost, and the negative material with the excellent chemical property such as specific capacity height, good cycling stability, good rate capability is necessary.
The patent application of Application No. 201510104614.9 entitled " preparation method of a kind of big size graphene/composite cathode material of silicon/carbon/graphite ", the preparation method of disclosed Graphene/composite cathode material of silicon/carbon/graphite is that the mixed acid process utilizing crystalline flake graphite to join sulphuric acid and nitric acid prepares graphite oxide, adds potassium permanganate and H2O2Preparation large scale graphene oxide further, the most sonicated mixture solution obtaining large scale graphene oxide and graphite, more annealed, obtain big size graphene composite cathode material of silicon/carbon/graphite.The lithium storage content of big size graphene/composite cathode material of silicon/carbon/graphite prepared by this method is 372mAhg-1～401mAhg-1, coulombic efficiency is 85%～90%, and under 5C multiplying power, capacity attenuation is 162mAhg-1, cycle performance is poor, and preparation technology is more complicated, and produces bigger environmental pollution.
The prior art close with the present invention is the patent application of Application No. 201510545536.6, " porous carbon of a kind of doped graphene/ferriferrous oxide nano fiber lithium cell cathode material and preparation method thereof ", it is to utilize electrostatic spinning technique preparation doping iron salt and the polyacrylonitrile/polymethyl methacrylate nano fiber of Graphene, is obtained the porous carbon/ferriferrous oxide nano fiber lithium cell cathode material of doped graphene by pre-oxidation and high temperature cabonization.The lithium storage content of the porous carbon of doped graphene prepared by this method/ferriferrous oxide nano fiber lithium cell cathode material is 720 mAhg-1～754mAhg-1, under 5C multiplying power, capacity attenuation is 480mAhg-1, cycle performance is poor, and Fe3O4Huge change in volume and serious particle aggregation can occur during embedding de-lithium, cause electric charge and transmission and diffusion poor, can make as negative material that the cyclical stability of battery is poor, high rate performance is the highest.
Nano diamond is important a kind of material with carbon element, not only hardness is high, intensity is big, chemical stability good, excellent heat conductivity, and specific surface area is big, surface activity is high, extensive application in the numerous areas such as composite deposite, precise polished, mechanical lubrication, drug loading, magnetic recording, electronic imaging.Nano diamond can use explosion method Nano diamond, generally uses graphite microparticles and explosive composition detonation under the conditions of negative oxygen to prepare.Use Nano diamond can increase the absorption of lithium, improve reversible capacity and lithium ion transport speed.Diamond nano-particles has the advantage stable, change in volume is little.Nano diamond and other carbon nanomaterials are made composite construction and introduces in lithium cell cathode, it will improve negative electrode and the performance of battery.
Summary of the invention
The technical problem to be solved in the present invention is, by selection and the design of special construction of functional material, traditional graphene material and diamond nano material are combined, it is thus achieved that a kind of chemical property is good, low cost, the electrode material of a kind of new construction of environmental protection.
The present invention uses microwave assisting method to prepare material with carbon element, by adding the nano-diamond powder of different quality ratio in the pre-reaction material of carbon, obtain the combination electrode material of a kind of nano-diamond powder and graphene nanometer sheet, to improving the storage lithium performance of material with carbon element further.
The concrete technical scheme of the electrode material of the present invention is as follows.
A kind of nano-diamond powder and graphene combination electrode material, is characterized in that, the laminated structure in multilamellar, surface exists corrugated fold, and Nano diamond grain adsorbs on graphene film surface；Nano-diamond powder is 0.066～0.334: 1 with the mass ratio of Graphene.
Described Nano diamond grain, grain size is 5～10nm.
Above-mentioned nano-diamond powder and the preparation of graphene combination electrode material have two kinds of method microwave assisting methods and direct mixing method.The concrete technical scheme of preparation method of electrode material is the most as described below.
Microwave assisting method prepares the technical scheme of nano-diamond powder and graphene combination electrode material: a kind of nano-diamond powder and the preparation method of graphene combination electrode material, citric acid and carbamide are dissolved in appropriate amount of deionized water formation colourless transparent solution, then nano-diamond powder is added, 30～60min are processed through high frequency ultrasound, gained solution is placed in microwave oven under 850W power heating 10～15min, and solution is eventually become dark-brown solid composite by the colourless yellowish-brown that becomes；900 DEG C of carbonization treatment 2 hours, the nano-diamond powder obtained and graphene combination electrode material under inert gas shielding again by the solid composite drying that obtains.
Wherein, citric acid can be 1: 3～4 with the mass ratio of carbamide；The ratio of the quality of nano-diamond powder and citric acid and urea quality sum is 0.005～0.025: 1.
Described solid composite drying, can be dried 1～2h under the conditions of 60～80 DEG C, to remove the moisture of residual.
Direct mixing method prepares the technical scheme of nano-diamond powder and graphene combination electrode material: a kind of nano-diamond powder and the preparation method of graphene combination electrode material, nano-diamond powder is mixed with Graphene in mass ratio 1: 3～4, in dehydrated alcohol, processes 6-8h through high frequency ultrasound；Then the suspension of Graphene with nano-diamond powder is dried under the conditions of 60 DEG C and evaporates completely to dehydrated alcohol, obtain nano-diamond powder/graphene combination electrode material.
Nano-diamond powder and graphene combination electrode material is used to make the negative electrode of lithium ion battery, detailed process is: nano-diamond powder and graphene combination electrode material is pulverized and grinds until powder granule size reaches nanoscale, the carbon black (helping conductive agent) used with lithium cell cathode mixes, at polyvinylidene fluoride (PVDF, binding agent) effect under grind, and add a certain amount of 1-Methyl-2-Pyrrolidone (NMP, solvent) so that becoming viscous fluid by magnetic stirrer；Viscous fluid is applied to collector, is dried at 120 DEG C；Finally it is cut into the negative electrode of the compound lithium ion battery of electrode shape compacting, prepared nano-diamond powder and Graphene.
Wherein, nano-diamond powder/graphene combination electrode material in mass ratio: Kynoar: white carbon black is 8: 1: 1；Described collector, is Copper Foil；It is dried at described 120 DEG C, is in 120 DEG C of vacuum drying ovens, be dried 12h.
The present invention further provides a kind of lithium ion half-cell: positive pole is with metal lithium sheet for electrode, nano-diamond powder/graphene composite material that negative pole prepares containing with good grounds said method in the environment of anhydrous and oxygen-free.Experimental measurements shows, the carbon composite of gained is used as lithium ion battery negative material specific discharge capacity after first charge-discharge circulates and reaches 1085mAhg-1, first charge-discharge efficiency is 60%, far above the theoretical circulation capacity 372mAhg of graphite-1.Along with the increase of cycle-index, discharge capacity has slightly decline, and the charge/discharge capacity after 50 circulations has reached 650mAhg-1, capability retention is 59.9%, and discharge and recharge coulombic efficiency is close to 100%.
The present invention utilizes nano-diamond powder/Graphene compound acquisition novel composite electrode material, the two forms cooperative effect, prepare high performance Novel pure carbon lithium ion cell negative electrode material, solve that the specific capacity of commercial graphite negative pole is low and the problem such as the high discharge platform of novel graphite alkene negative pole, low coulombic efficiency first；Nano-diamond powder not only hardness is high, excellent heat conductivity, and specific surface area is big, Stability Analysis of Structures, when as lithium cell cathode material, the capacity fade problem that can avoid drastically changing of volume in charge and discharge process and cause, and the big specific surface area of nano-diamond powder is of value to the storage of lithium ion, for improving the specific capacity of negative material, the cyclical stability kept is most important.It is simple that the nano-diamond powder of the present invention and the preparation method of graphene combination electrode material have process, with low cost, it is easy to accomplish, the advantage such as easy amplification, it is expected to following large-scale production.
Accompanying drawing explanation
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# is for lithium ion battery negative charge/discharge capacity perseverance circulation performance comparison figure.
Fig. 6 is that sample 1# and 4# is for lithium ion battery negative charge/discharge capacity zoom rate cycle performance comparison diagram.
Fig. 7 is sample 1# charge and discharge cycles volt-ampere test figure.
Fig. 8 is sample 1# perseverance rate charge-discharge curve test figure.
Fig. 9 is sample 4# charge and discharge cycles volt-ampere test figure.
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#.
Detailed description of the invention
The application is described in further detail with embodiment below in conjunction with accompanying drawing, it should be pointed out that embodiment described below is intended to be easy to the understanding to the application, and it does not play any restriction effect.
Embodiment 1: prepared by the microwave assisting method of nano-diamond powder/graphene nanometer sheet combination electrode material
2g citric acid and 6g carbamide are dissolved in 30ml deionized water (20～40ml) and form colourless transparent solution, then add 0.16g grain size be 5～10nm nanometers bortz powder (addition of nano-diamond powder account for citric acid, carbamide, the 1.9% of nano-diamond powder mixture quality～2.0%), 30～60min are processed through high frequency ultrasound, gained solution is placed in microwave oven under 850W power heating 10min, and solution is eventually become dark-brown solid reaction terminated by the colourless yellowish-brown that becomes.Then the solid composite obtained is moved to vacuum drying oven, under the conditions of 60 DEG C, be dried 1h, to remove the moisture of residual in molecule.Dried solid composite being pulverized and is ground to powder, powder granule is less than 10 μm, to increase the specific surface area of material.Put into tube furnace, under noble gas argon shield, carry out carbonization treatment, calcine 2 hours for 900 DEG C.The carbon complex now obtained is become black blocks of solid from original dark-brown, continues to pulverize and grind 3～4h, until powder granule size reaches nanoscale.Prepared nano-diamond powder/graphene combination electrode material sample is labeled as sample 4#.
As the nano-diamond powder 0.16g of raw material in the present embodiment, it is held essentially constant after being prepared as nano-diamond powder/graphene combination electrode material, or slightly reduces.The mixture that carbon complex is nano-diamond powder and Graphene finally given through carbonization is through weighing as 0.76g, and the quality calculating Graphene is about 0.6g, i.e. nano-diamond powder is 0.26: 1 with the mass ratio of Graphene.
The transmission electron microscope picture of sample 4# is shown in that Fig. 2, X-ray diffraction (XRD) spectrum is shown in that Fig. 3, Raman spectrum are shown in Fig. 4.With the used as negative electrode of Li-ion battery of sample 4# making in lithium ion battery, embodiment 4 is shown in its performance test.
X-ray diffraction (XRD) material phase analysis of the present embodiment sample 4# is carried out on the polycrystalline XRD instrument of XRD-6000, Cu target, K α radiation source (λ=0.15418nm).The XRD figure spectrum of Fig. 3 it can be seen that 2 more obvious peaks, lays respectively near 2 θ=26 ° and 44 °, (002) face of corresponding six purpose square graphites and (101) face.Show that sample 4# has graphite-structure.The diffraction maximum peak shape of sample 4# is sharp-pointed, and signal is also preferable, shows the good crystallinity of sample 4#.The Raman spectrum (Raman) of the present embodiment sample 4# is analyzed and is carried out on Renishaw inVia type copolymerization Jiao's micro-Raman spectroscopy, and light source is Ar+Laser, wavelength is 514.5nm.As shown in Figure 4, sample 4# is at (800-2000) cm for Raman result-1Between exist two obvious characteristic peaks, be 1350cm respectively-1Neighbouring D peak and 1580cm-1Neighbouring G peak.At 2650-3000cm-1Second order Raman peaks (i.e. 2D peak) is had on interval.The morphology analysis of the present embodiment sample 4# is used JEM-2200FS Flied emission transmission electron microscope.The transmission electron microscope picture of the sample 4# that Fig. 2 is given.Fig. 2 shows fine and close the adsorbing on the graphene film surface of fold of Nano diamond grain; substantial amounts of Nano diamond grain can improve the specific surface area (shown in Figure 11 N2 adsorption BET specific surface area test curve) of sample; and Nano diamond particles benefit is in improving the memory density of lithium ion and transfer rate, can be as the preferable lithium ion battery material of one.
The preparation of the pure grapheme material of embodiment 2 (not adding nano-diamond powder) microwave assisting method
The proportioning raw materials (being not added with nano-diamond powder) of embodiment 1 and technical process is used to prepare pure grapheme material as comparative example.Particularly:
Citric acid 2g and carbamide 6g is dissolved in 30ml deionized water formation colourless transparent solution, 30～60min are processed through high frequency ultrasound, gained solution is placed in microwave oven under 850W power heating 10min, and solution is eventually become dark-brown solid reaction terminated by the colourless yellowish-brown that becomes.Then the solid product obtained is moved to vacuum drying oven, under the conditions of 60 DEG C, be dried 1h.Dried solid product being pulverized and is ground to powder, powder granule is less than 10 μm.Put into tube furnace, under argon shield, carry out carbonization treatment, calcine 2 hours for 900 DEG C.The carbonized solid product obtained continues to pulverize and grind 3～4h, until powder granule size reaches nanoscale.Prepared pure grapheme material sample is labeled as sample 1#.
Sample 1# is as a comparison sample to make comparisons with sample 4#, and result is as follows.
The XRD result of sample 1# as it is shown on figure 3, XRD figure spectrum it can also be seen that 2 more obvious peaks, lays respectively near 2 θ=26 ° and 44 °, (002) face of corresponding six purpose square graphites and (101) face.Show that sample 1#, 4# are respectively provided with graphite-structure.In collection of illustrative plates, the sample 4# diffraction maximum peak shape than sample 1# is more sharp-pointed, and signal is the best, shows that the crystallinity of sample 4# compares sample 1# some higher, and the material of sample 4# has good layer structure, is more suitable for embedding and the abjection of lithium ion.As shown in Figure 4, sample 1# is also at (800-2000) cm to Raman spectrum (Raman) analysis result of sample 1#-1Between all there are two obvious characteristic peaks, be 1350cm respectively-1Neighbouring D peak and 1580cm-1Neighbouring G peak.At 2650-3000cm-1Second order Raman peaks (i.e. 2D peak) is had on interval.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 the laminated structure of multilamellar, and surface exists a certain degree of fold, such as corrugated.With the used as negative electrode of Li-ion battery of sample 1# making in lithium ion battery, embodiment 5 is shown in its performance test.In embodiment 5 it can be seen that the used as negative electrode of Li-ion battery that makes of sample 4# in the performance of lithium ion battery than sample 1# outstanding a lot.
Prepared by the microwave assisting method of embodiment 3 nano-diamond powders/graphene nanometer sheet combination electrode material
Interpolation 0.04g it is dissolved in 30ml deionized water respectively at 2g citric acid and 6g carbamide, 0.08g, 0.20g grain size is the bortz powder of 5～10nm nanometers, (addition of nano-diamond powder accounts for citric acid, carbamide, the 0.5% of nano-diamond powder mixture quality, 1.0%, 2.5%), process through high frequency ultrasound similarly to Example 1, microwave-oven-heating, vacuum drying oven is dried, pulverize grinding, carbonization treatment is carried out under noble gas argon shield, continue to pulverize and grind, nano-diamond powder/graphene combination electrode material the sample prepared is labeled as sample 2#, sample 3#, sample 5#.
Sample 2#, sample 3#, sample 5# are about 0.6g through weighing the quality calculating Graphene, the mass conservation of nano-diamond powder before and after reaction, learns that in sample 2#, sample 3#, sample 5#, the mass ratio of nano-diamond powder and Graphene is respectively 0.066: 1,0.13: 1,0.33: 1.
Sample 2#, sample 3#, sample 5# all can be as the negative materials of lithium ion battery.
Prepared by the electrode material that embodiment 4 nano-diamond powder directly mixes with Graphene
Present embodiments provide another method preparing Nano diamond/Graphene electrodes to the present invention.Directly being mixed with Graphene in mass ratio 1: 3～4 by nano-diamond powder, process 6-8h through high frequency ultrasound in dehydrated alcohol, make that the two mixes is more abundant.Then the suspension of Graphene Yu nano-diamond powder is moved to vacuum drying oven, be dried until dehydrated alcohol evaporates completely under the conditions of 60 DEG C.Finally dried solid mixture pulverized and be fully ground to powder.Nano-diamond powder/the graphene combination electrode material obtained is designated as sample 6#.
Figure 12 is the sample 6# transmission electron microscope picture that the Graphene of commercialization prepares with the batch mixing of nano-diamond powder, as can be seen from the figure Nano diamond grain dispersion is on graphene film surface, form nano-diamond powder/graphene combination electrode material, obtain and the close result of embodiment 1 and 2.
Embodiment 5 nano-diamond powder/graphene nanometer sheet composite makes the negative pole of lithium ion battery
Lithium ion battery negative uses the conductive agent white carbon black mixing that helps of 80wt% Nano diamond/graphene composite material (active substance), the binding agent (Kynoar, PVDF) of 10wt% and 10wt% to constitute.Loading after three mixed grinding 0.5h in container, in container, a certain amount of 1-Methyl-2-Pyrrolidone of interpolation (NMP, solvent) is positioned on magnetic stirring apparatus again and at the uniform velocity stirs 6h, so that mixture is viscous fluid.Using Copper Foil as collector, being applied on Copper Foil by above-mentioned mixing dope, coating density needs uniformly.The temperature of vacuum drying oven is arranged on 120 DEG C, and takes above-mentioned Copper Foil smear and be placed in drying baker, after timing 12h, take out stand-by.The Copper Foil smear special cutter mould that will prepare, is cut into several electrode disks, after with tablet machine compacting pole piece on active material so that it is be fully contacted with collector, anti-anti-avulsion material.
Embodiment 6: the making of lithium ion battery and performance test
With sample 1#, 4# as Typical Representative, test its performance for lithium ion battery.With the sample 1# of pure graphene nanometer sheet as comparative sample.Lithium ion battery prepared by this test is CR-2025 type button cell.Negative material uses the conductive agent white carbon black mixing that helps of 80wt% active substance, the binding agent (Kynoar, PVDF) of 10wt% and 10wt% to constitute, using Copper Foil as collector.The Copper Foil smear special cutter mould that will prepare, is cut into several electrode disks, after with tablet machine compacting electrode slice on active material so that it is be fully contacted with collector.Then electrode slice quality is weighed, in case the specific capacity parameter etc. of calculated for subsequent.Taking supporting battery plus-negative plate shell, pad, shell fragment and polypropylene diaphragm, electrolyte, electrode slice etc., according to the making predetermined operation of lithium battery, safe and orderly operation in glove box, encapsulates battery.It is respectively labeled as S1, S2 for the battery obtained by cathode of lithium battery active material with sample 1#, 4#.
1) charge-discharge magnification test
Battery S1, the S2 prepared in testing example 3 in blue electrical testing system.At 25 DEG C, it is discharged to 0.02V according to certain discharge current；After electric discharge terminates, battery standing 3 minutes；Then with certain electric current density constant-current charge to 3V, charging terminate after, battery standing after 3 minutes with identical electric current density constant-current discharge to 0.02V；Battery stands 3 minutes after completely filling, then with identical condition charging.Electrochemical property test result is as it is shown in figure 5, as can be seen from the figure electric discharge first and the charge specific capacity of sample 4# have respectively reached 1085mAhg-1And 749mAhg-1, discharging efficiency is 61% first, and along with the increase of cycle-index, discharge capacity has small size decline, and the charge/discharge capacity of the 50th circulation is 646mAhg-1, close to 2 times of graphite theoretical capacity, discharge and recharge coulombic efficiency is close to 100%.The circulation volume first of sample 1# is respectively 874.7mAhg-1And 444.2mAhg-1, discharging efficiency is 51% first, and after stable circulation, capacity is maintained at 300mAhg-1Near, coulombic efficiency is also close to 100%.The capacity of this Capacity Ratio sample 4# is low.
Become multiplying power discharging, be set as 0.2C, 0.5C, 1C, 5C, 10C successively, battery S1, S2 are charged reversible specific capacity test.Electrochemical property test result is as shown in Figure 6.As seen from the figure, under the battery S2 change rate charge-discharge situation that nano-diamond powder/graphene nanometer sheet composite (sample 4#) is prepared, all there are good specific capacity and conservation rate, it is shown that excellent chemical property.
2) charge and discharge cycles volt-ampere test
Cyclic voltammetry condition controls at 25 DEG C for test temperature, Applied Electrochemistry work station, and arranging scanning speed is 0.1mV/s, and selecting sample 1#, 4# is electrode active material.Such as Fig. 7, the cyclic voltammetry curve that sets forth front 5 circulations in 8, it can be seen that in addition to having special peak in circulation for the first time and occurring, after second time 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 positioned at the generation of solid electrolyte interface film (SEI) of the wide characteristic peak correspondence in 0.3V to 1.0V place.SEI film is during lithium ion battery first charge-discharge, electrode material and electrolyte react on solid-liquid phase interface and form one layer of passivation layer being covered in electrode material surface, this passivation layer can stop the further reaction of electrolyte, thus improves the stability of battery.The more stable SEI film that the electrode having Nano diamond is formed, is conducive to obtaining the battery of good characteristic
3) permanent rate charge-discharge curve test
The permanent rate charge-discharge curve of battery S1, S2 of preparing for electrode active material with sample 1#, 4# respectively such as Fig. 9, shown in 10, multiplying power size is 0.2C, and voltage range is 0.02-3V, gives representational 5 curves in figure.In first time charging and discharging curve, it can be seen that have an obvious discharge platform near 0.6V, the corresponding SEI peak of CV curve.In circulation subsequently, charge/discharge capacity tends towards stability.This shows that the irreversible loss of capacity occurs mainly in first time charge and discharge process.The circulation volume first of sample 1# is respectively 874.7 and 444.2mAhg as shown in Figure 9-1, discharging efficiency is 51% first, and from figure, 10 can be seen that the electric discharge first of sample 4# and charge specific capacity have respectively reached 1085 and 749mAhg-1, far above the theoretical capacity 372mAhg of graphite-1, irreversible capacity is 336mAhg-1, discharging efficiency is 61% first, higher than sample 1#.Charging and discharging curve, almost without change, shows have preferable cyclical stability.In sum, the battery S2 that nano-diamond powder/graphene nanometer sheet composite (sample 4#) the is prepared battery S1 that relatively (sample 1#) is prepared all has good specific capacity and conservation rate, it is shown that excellent chemical property.
Claims (7)
1. nano-diamond powder and a graphene combination electrode material, is characterized in that, the lamellar knot in multilamellar
Structure, there is corrugated fold in surface, Nano diamond grain adsorbs on graphene film surface；Nano-diamond powder with
The mass ratio of Graphene is 0.066～0.334: 1.
Nano-diamond powder the most according to claim 1 and graphene combination electrode material, is characterized in that,
Described Nano diamond grain, grain size is 5～10nm.
3. the nano-diamond powder of claim 1 and a preparation method for graphene combination electrode material, will
Citric acid and carbamide are dissolved in appropriate amount of deionized water formation colourless transparent solution, then add Nano diamond
Powder, processes 30～60min through high frequency ultrasound, gained solution is placed in microwave oven under 850W power heating
10～15min, solution is eventually become dark-brown solid composite by the colourless yellowish-brown that becomes；By consolidating of obtaining
Nanocrystal composition drying 900 DEG C of carbonization treatment 2 hours, the Nano diamond obtained under inert gas shielding again
Powder and graphene combination electrode material.
Nano-diamond powder the most according to claim 3 and the preparation method of graphene combination electrode material,
It is characterized in that, citric acid is 1: 3～4 with the mass ratio of carbamide；The quality of nano-diamond powder and citric acid with
The ratio of urea quality sum is 0.005～0.025: 1.
5. the nano-diamond powder of claim 1 and a preparation method for graphene combination electrode material, will
Nano-diamond powder mixes, in dehydrated alcohol at high frequency ultrasound with Graphene in mass ratio 1: 3～4
Reason 6～8h；Then the suspension of Graphene Yu nano-diamond powder is dried to dehydrated alcohol under the conditions of 60 DEG C
Evaporate completely, obtain nano-diamond powder/graphene combination electrode material.
6. the nano-diamond powder of claim 1 and a purposes for graphene combination electrode material, be used for making
Make the negative electrode of lithium ion battery；Detailed process is: nano-diamond powder and graphene combination electrode material are ground
Broken and grinding reaches nanoscale until powder granule size, mixes with carbon black, under the effect of polyvinylidene fluoride
Grind, and add 1-Methyl-2-Pyrrolidone so that becoming viscous fluid by magnetic stirrer；By thickness stream
Body is applied to collector, is dried at 120 DEG C；Finally be cut into electrode shape compacting, prepare nano-diamond powder and
The negative electrode of the lithium ion battery that Graphene is compound.
Nano-diamond powder the most according to claim 6 and the purposes of graphene combination electrode material, its
Feature is, in mass ratio nano-diamond powder/graphene combination electrode material: Kynoar: white carbon black is 8:
1∶1；Described collector, is Copper Foil；It is dried at described 120 DEG C, is in 120 DEG C of vacuum drying ovens
It is dried 12h.
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