CN103570002A - Electrochemical graphene and its electrode composites and lithium batteries - Google Patents
Electrochemical graphene and its electrode composites and lithium batteries Download PDFInfo
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- CN103570002A CN103570002A CN201210254481.XA CN201210254481A CN103570002A CN 103570002 A CN103570002 A CN 103570002A CN 201210254481 A CN201210254481 A CN 201210254481A CN 103570002 A CN103570002 A CN 103570002A
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Abstract
The invention provides electrochemical graphene ECG (EC-graphene), which is high-quality graphene produced by an electrochemical stripping method. The invention also provides an electrode composite material and a lithium battery thereof, wherein the electrochemical graphene mixed in the positive and negative electrode materials of the lithium battery or the surface modified positive and negative electrode materials of the lithium battery can greatly improve the electric capacity of the lithium battery under heavy current discharge and the cycle life of the battery, and improve the power and the energy density of the positive and negative electrode materials.
Description
Technical field
The present invention relates to a kind of electrochemistry Graphene and the electrode composite material that comprises described electrochemistry Graphene and lithium cell.
Background technology
Because the earth continues to warm, tsunami, the oil in Japan and South Asia peter out and the danger and disaster such as Nuclear Safety, now very urgent to the requirement of environment protection and carbon reduction.Japan, China and European and American countries have been started to develop new forms of energy and accumulator system at present, and by developing power truck and oily electric hybrid vehicle to reduce the dependency to oil.The in the situation that of the equal dependence on import of the most of energy in Taiwan, for naturally more not falling behind in the exploitation of new energy resources system and material.
Yet, the major cause that at present power truck also cannot replace petrol and diesel oil car be completely power truck cost far above petrol and diesel oil car, and the pure electric vehicle duration of charging need the more than ten times of petrol and diesel oil car refueling time.In addition, power truck power and steaming range also seem not enough than petrol and diesel oil car.In recent years, because lithium cell has advantages of high-energy-density, post hope and can replace gradually the major impetus source that traditional nickel metal hydride battery becomes power truck of future generation, but lithium cell cost is far above traditional nickel hydrogen battery.Research is at present found Graphene to be applied in lithium battery material, can make up the duration of charging long, and can under large electric current, promote lithium cell power and steaming range.
The known technology that is used for manufacturing Graphene comprises the methods such as mechanically peel method (mechanical exfoliation), epitaxial growth method (epitaxial growth), chemical Vapor deposition process (chemical vapor deposition, CVD) and chemical stripping method (chemical exfoliation).Although use mechanically peel method and epitaxial growth method can generate the good Graphene of quality, these two kinds of methods all cannot big area synthesizing graphite alkene; Chemical Vapor deposition process and chemical stripping rule, because cost is expensive, are therefore applied to obviously have any problem in battery of electric vehicle material.Therefore, still need at present a kind of method that can scale of mass production Graphene, for battery material powder factory or battery manufacturers, carry out battery material reprocessing (surfaction) or directly mix sizing process, expectation promotes cycle life and power and the steaming range of lithium cell with lower material cost, and then reduces the cost of electric vehicle lithium battery.
The application of Graphene on lithium cell at present had many academic papers and Patents, but great majority are to utilize Hu Moer method (Hummers'method) to make graphene oxide (Graphene oxide, GO), then by the GO solution disperseing and precursor (precursor) combination of lithium cell positive and negative pole material.Periodical literature materials chemistry magazine (Journal of Materials Chemistry, 2011,21,3353) discloses lithium iron phosphate positive material (LiFePO
4) calcination at 600 ℃ or higher temperature of precursor and GO solution, GO can be reduced into Graphene, by the calcination of anode material of lithium battery precursor, be the matrix material of anode material of lithium battery and Graphene simultaneously, or the matrix material of the anode material of lithium battery of graphene coated.
In addition, periodical literature american chemical association application material and interface (ACS Appl.Mater.Interfaces2011,3,2966-2972) disclose similar chemical stripping Graphene synthetic method (Chemically-exfoliated grapheme, ECG, claim again graphite delamination method), and disclose by the prepared Graphene of chemical stripping method can with such as Li-Ni-Mn-Co-O (LiNi
1/3co
1/3mn
1/3o
2) etc. anode material of lithium battery combination, to form matrix material.The Graphene that described synthetic method is produced need account for the approximately 5wt% of integral battery door material content to 10wt%, just can reach the chemical property of lithium cell under heavy-current discharge.
United States Patent (USP) the 7th, discloses a kind of lithium cell cathode material preparation method for 745, No. 047B2, and it is the precursor of GO is mixed from different negative material and heat peel off/reduced graphene.Yet chemical stripping Graphene technique needs more chemical step, more easily causes environmental pollution, and described Graphene quality is easy to be subject to the impacts such as raw material state, stripping process and reductive condition, and therefore described technique is difficult to stable control.Therefore,, when described method is applied to the lithium cell positive and negative pole material (ECG-surface modified cathode and anode materials) of industrialization volume production chemical stripping Graphene surfaction, its product performance will be difficult to maintain.
Therefore, still need at present a kind of method of with low cost and simple process, with the electrode material of lithium battery of preparing high-quality graphene and comprising high-quality graphene.
Summary of the invention
In view of above-mentioned problem, the object of this invention is to provide a kind of low cost, simple flow and produce fast containing high quality electrochemistry Graphene.
In the present invention, term " electrochemistry Graphene " (ECG) refers to that applicant is at No. 100115655 prepared Graphene of exposure method of Taiwan patent application case, and the specification sheets of described application case is now incorporated to herein as reference.Described electrochemistry Graphene is to make with electrochemical method, and described method comprises and the first electrode and the second electrode is set in electrolytic solution, and the ion in described electrolytic solution is as insert (insert), and described the first electrode is graphite material; Under the first bias voltage, carry out the embedding step of graphite material; And under the second bias voltage, utilizing described insert to carry out the strip step of graphite material, the solid part finally taking out in electrolytic solution is electrochemistry Graphene.According to described method gained electrochemistry Graphene, its oxygen level is far below the Graphene through chemical stripping method gained (ECG), therefore electrochemistry graphene conductive, far above chemical stripping Graphene (ECG), and is conducive to increase the conduction velocity of electronics.From the above, the invention provides a kind of electrochemistry Graphene of novelty, it has oxygen level, more than 90% penetration and the sheet resistance below 10k Ω/sq below 20wt%, and wherein said sheet resistance is to take the thickness of electrochemistry Graphene to arrive 5nm as 1.5nm.
The definition of above-mentioned " below 20% " comprises the Any Digit of wherein containing, for example, be below 18%, below 16%, below 13%, or the scope such as approximately 2% to 18%, 4% to 16%, 6% to 14% and 8% to 12%.In the same manner, the definition of above-mentioned " more than 90% " comprises the Any Digit of wherein containing, and for example approximately 87%, 89%, 91%, 93%, 95%, 97% or 99% with first-class scope.In the same manner, the definition of above-mentioned " 10k Ω/sq following " comprises the Any Digit of wherein containing, and for example about 9k Ω/sq is following, 8k Ω/sq is following, 7k Ω/sq is following, 6k Ω/sq is following, 5k Ω/sq is following, 4k Ω/sq is following, 3k Ω/sq is with inferior scope.The definition of above-mentioned " 1.5nm is to 5nm " comprises the Any Digit of wherein containing, such as 1.5nm to 3nm, 2nm to 4nm, 2.5nm to 4.5nm or 3nm to scopes such as 5nm.With above-mentioned, other digital scope also includes the Any Digit scope wherein containing herein.
In the methods of the invention, described electrochemistry Graphene can further pass through following process or upgrading, for example, with physics or chemical process, described electrochemistry Graphene is adulterated or mix nitrogen or other non-carbon.
Another object of the present invention is to provide a kind of novel use of above-mentioned electrochemistry Graphene, and it is for the preparation of lithium cell.
Another object of the present invention is to provide a kind of lithium cell, and it comprises above-mentioned electrochemistry Graphene and electrode materials or electrode material precursor.
According to lithium cell of the present invention, wherein in the amount of described electrode materials or electrode material precursor, described electrochemistry Graphene accounts for the utmost point low levels of integral battery door material, can reach splendid charge discharge performance.If tradition lithium cell has higher Graphene content, its charge discharge performance is better.General the used lithium cell of academic journal article approximately contains the Graphene of 5wt%, by contrast, according to the amount of the required Graphene of lithium cell of the present invention, can be 0.001wt% to 5wt%, or 0.001wt% is to 2wt%, or 0.01wt% is to 1wt%, can reach splendid charge discharge performance.Above-mentioned " 0.001wt% is to 5wt% " also comprises the Any Digit scope wherein containing, such as 0.05wt% to 1.5wt% or 0.03wt% to scopes such as 1.2wt%.
Described electrochemistry Graphene system and described electrode materials or electrode material precursor carry out mechanically mixing (mechanical mixing), physics or chemical process surfaction (surface modification) or doping (doping).In embodiments of the present invention, described mechanically mixing comprises ultrasonic vibration or intimate mixing.
According to lithium cell of the present invention, compare with the lithium cell that does not add electrochemistry Graphene, the chemical property under large electric current charge/discharge can have remarkable lifting, and the lithium cell positive and negative pole material of electrochemical stripping Graphene institute blending, without follow-up high-temperature technology, therefore have advantages of with low cost.
In the specific embodiment of the invention, for lithium metal, be the button cell (coin cell) that counter electrode forms, carry out that different electric currents discharge and recharge and cycle life test.According to lithium cell of the present invention, its integral battery door material only needs the electrochemistry Graphene of utmost point low levels, can reach the lithium battery chemical property identical or more superior with high-content chemical stripping Graphene (ECG).
According to lithium cell of the present invention, wherein said electrode materials or electrode material precursor comprise positive electrode material and/or negative material or its precursor, and described positive electrode material or its precursor include, but is not limited to the (LiFe of lithium iron system
(1-x)m
xp
(1-x)o
2 (2-x), 0≤X<1), be preferably lithium iron system, lithium iron phosphorus or Lithium Oxide 98min iron phosphorus; Lithium-cobalt system (LiCoO
2); (the LiMn of lithium manganese system
2o
4); (the LiNiO of lithium nickel system
2), lithium cobalt manganese nickel three component system (NCM) and oxide compound or its mixture; Described negative material or its precursor include, but is not limited to carbon material, stupalith, silicon (silicon), tin (Tin) and other metal and metal oxide and composition thereof, and wherein said carbon material includes, but is not limited to carbon fiber or its mixture of natural and electrographite, soft carbon, hard carbon, carbon nanotube (CNT), vapor deposition carbon fiber (VGCF), other form.In aspect enforcement of the present invention, described positive electrode material is iron lithium phosphate (LiFePO
4, LFP).
According to lithium cell of the present invention, can further comprise additive, it is optional from assistant director of a film or play's agent, tackiness agent, carbon material or solvent or its combination.In aspect enforcement of the present invention, described assistant director of a film or play's agent includes, but is not limited to conductivity carbon black (trade(brand)name Super P) and original synthetic graphite (trade(brand)name KS6); Described tackiness agent includes, but is not limited to poly(vinylidene fluoride) (PVDF, Polyvinylidene fluoride), carboxymethyl cellulose (CMC, Carboxymethyl Cellulose), styrene/butadiene copolymers (SBR, Styrene Butadiene Copolymer); Described carbon material includes, but is not limited to natural and electrographite, soft carbon, hard carbon, carbon nanotube (CNT, Carbon nanotubes), carbon fiber or its mixture of vapor deposition carbon fiber (VGCF, Vapor Grown Carbon Fiber), other form; Described solvent can be selected from METHYLPYRROLIDONE (NMP, N-Methyl-2-pyrrolidone) etc.
Another object of the present invention is to provide a kind of preparation method of novel lithium cell, and it comprises the following step:
Above-mentioned electrochemistry Graphene and electrode materials or electrode material precursor are carried out to mechanically mixing, physics or chemical process surfaction or doping; And
The product of abovementioned steps gained is carried out to drying-granulating.
In aspect enforcement of the present invention, described mechanically mixing comprises ultrasonic vibration or intimate mixing.
In aforesaid method of the present invention, amount in described electrode materials or electrode material precursor, described electrochemistry Graphene accounts for integral battery door material utmost point low levels, can make lithium cell reach splendid charge discharge performance, the amount of wherein said Graphene can be 0.001wt% to 5wt%, or 0.001wt% is to 2wt%, or 0.01wt% is to 1wt%.
In aforesaid method of the present invention, described drying-granulating step includes, but is not limited to heat drying granulation (heatdrying), spray drying granulation (spray drying) or suction filtration drying-granulating (filter drying).
In aspect enforcement of the present invention, heat drying granulation step is will after solvent evaporation, to leave powder in baking oven or on hot-plate.
In aspect enforcement of the present invention, spray drying granulation step is that wherein said solution comprises the solvent that selects free dimethyl phthalate (DMP), N-Methyl pyrrolidone (NMP), acetonitrile or alcohols or its combination by electrochemistry Graphene and lithium cell positive and negative electrode matrix material solution intimate mixing.Peristaltic pump is evacuated to spraying disc and nozzle (spray disc or Nozzle) by described matrix material solution, nozzle entrance is set as to fixed temperature, and described temperature in is to design according to different solvents.In aspect enforcement of the present invention, described temperature in can be set as 100 ℃ to 200 ℃.After described matrix material solution being thrown away with high-revolving centrifugation, via the dry powder that forms of well heater, then via entrance high temperature, accelerate granulation process and carry out volume production.
Figure 10 shows the specific embodiment party face of spray drying granulation step of the present invention, according to electrochemistry Graphene of the present invention and lithium cell positive and negative pole material or its precursor, is to stir under clarifixator (S05), forms homogeneous solution (S07).Described homogeneous solution (S07) is via pipeline (S08), to be evacuated to spraying disc and nozzle (S09) by peristaltic pump (S06), and after throwing away under high-revolving centrifugation, via well heater (S10), be dried and form powder, and collecting with powder collection cavity (S11).Last gained powder accelerates granulation process via entrance high temperature and carrys out volume production.
In aspect enforcement of the present invention, suction filtration drying-granulating step is by electrochemistry Graphene and lithium cell positive and negative electrode matrix material solution intimate mixing, forms bulk material, then dry granulation process via suction filtration process.
At present granulation process is in the industry to spray that to be dried be main, because it can reach maximum production capacity, approximately monthly can produce the lithium cell positive and negative pole material of the electrochemistry Graphene upgrading/blending of 100 tons to 200 tons.
In aspect enforcement of the present invention, the particle of described drying-granulating step gained is further mixed and made into slurry with additive, and coat in copper aluminium foil collector plate, to make button cell, the optional free assistant director of a film or play's agent of wherein said additive, tackiness agent, carbon material or solvent or its combination.In aspect enforcement of the present invention, described carbon material includes, but is not limited to carbon fiber or its mixture of natural and electrographite, soft carbon, hard carbon, carbon nanotube (CNT), vapor deposition carbon fiber (VGCF), other form.
Another object of the present invention is to provide a kind of electrode composite material, and it comprises graphite, nano silicon particles and above-mentioned electrochemistry Graphene.
Accompanying drawing explanation
Fig. 1 is that electrochemistry graphene coated or intercalation are at the schematic diagram of whole lithium cell positive and negative pole material and other additive.
Fig. 2 is under different discharging conditions, has the cycle life electric capacity spirogram of the LiFePO 4 of anode material (LFP) of different electrochemistry Graphene content.
Fig. 3 is the C-rate of LiFePO 4 of anode material and the comparison diagram of electrical capacity with different electrochemistry Graphene content.
Fig. 4 be have the positive electrode material of 0.013wt% and 0.8wt% electrochemistry Graphene with not containing the commercial positive electrode material of electrochemistry Graphene at the continuously tested cycle life comparison diagram fixedly discharging and recharging under condition.
Fig. 5 is commercial graphite cathode charging and discharging curve figure.
Fig. 6 is the hybrid composite charging and discharging curve figure having lower than 1% silicon and electrochemistry Graphene and commercial Graphite Electrodes.
Fig. 7 is the cycle life electric capacity spirogram of graphite under different discharging conditions.
Fig. 8 is the cycle life electric capacity spirogram of ECG/Si/ graphite under different discharging conditions.
Fig. 9 is the comparison diagram of graphite and ECG/Si/ graphite electrical capacity under different discharging conditions.
Figure 10 is mist projection granulating schematic diagram.
Embodiment
In this article, unless be particularly limited, singulative " " and " described " also comprise its plural form.Any and all embodiment and exemplary term (for example, as " ") object are only for more outstanding the present invention herein, not for scope of the present invention, be construed as limiting, the term in this case specification sheets should not be regarded as implying that any not assembly of request can form the necessary assembly of implementing when of the present invention.
Hereinafter with reference to correlative type, electrochemistry Graphene is described according to the preferred embodiment of the invention and comprises electrochemistry Graphene electrodes material or lithium cell, wherein identical element is illustrated the reference marks with identical.
Fig. 1 is that electrochemistry graphene coated or intercalation are at the schematic diagram of whole lithium cell positive and negative pole material and other additive.The present invention is usingd commercial lithium iron phosphate positive material or other commercial positive electrode material as electrode materials (S03) and is not added electrochemistry Graphene (S01) as anode composite material comparative example.Described comparative example is containing assistant director of a film or play's agent (S02) of the positive electrode material of 80wt%, the tackiness agent of 10wt% (S04) and 10wt%, and in solvent NMP intimate mixing, the solids content of described comparative example is controlled at approximately 40% to 50%.Described anode composite material slurry rolls to prepare lithium battery device after coating in aluminum foil current collector.Described lithium battery device be with lithium metal as negative pole, carga moral (Celgard) PP/PE/PE of take is barrier film, and with 1M LiPF
6(lithium hexafluoro phosphate, Lithium hexafluorophosphate) ethylene carbonate (EC, Ethylene carbonate)/Methyl ethyl carbonate (EMC, Ethyl methyl carbonate)/methylcarbonate (DMC, Dimethyl carbonate) (1:1:1wt%)+1% vinylene carbonate (VC, Vinylene carbonate) is electrolytic solution.Described button cell (model 2032) is carried out to electrochemical measurement.
In specific embodiments of the invention, the electrochemistry graphene solution that described lithium cell comprises commercial positive electrode material and constant concentration, the ratio that described electrochemistry Graphene content accounts for integral battery door material is 0.01wt% and 0.13wt%, and the ratio in 80% positive electrode material is about 0.0135wt% and 0.158wt%.After intimate mixing, carry out the lithium cell positive and negative electrode composite powder that drying-granulating step can obtain electrochemistry Graphene upgrading or blending.The additives (the about 8:1:1 of ratio) such as described powder and tackiness agent, assistant director of a film or play's agent and solvent carry out intimate mixing, and the solid content of gained slurry is to be controlled at approximately 40% to 50%.Subsequently described slurry is coated in aluminum foil current collector, rolls to prepare the button cell device identical with comparative example to carry out electrochemical measurement.
The emphasis of electrochemical measurement and method are with constant current, under different charge-discharge velocities and constant voltage, to measure (CC-CV), its voltage range be 2V to 3.8V, constant voltage at 3.8V until electric current is less than 0.05C.Electrochemical measurement experiment can be learnt and add the electrical capacity difference that electrochemistry Graphene (S01) causes thus.
Fig. 2 represents to utilize the commercial LiFePO 4 of anode material button cell made with adding positive electrode material after the electrochemistry Graphene of different content, carries out the comparison diagram of chemical property under different charge-discharge velocities.As shown in Figure 2, add on a small quantity electrochemistry Graphene and can significantly promote the electrical capacity of positive electrode material under large electric current.Under 28C discharging condition, positive electrode material according to the present invention is than commercial positive electrode material, and can reach 50% electrical capacity is approximately 75 to 80mAh/g, and significantly promotes its battery cycle life.
Under fixing discharging current, calculate complete discharge time and be converted into actual C-rate, can relatively add the impact on electrical capacity under different C-rate of electrochemistry Graphene.Fig. 3 is presented under the condition of rapid discharge, and the battery with a small amount of electrochemistry Graphene can reach higher electrical capacity conservation rate.Result is known thus, and the electrochemistry Graphene that adds minute quantity contributes to promote the energy density of battery material under large electric current.Therefore, the present invention can be applicable to power truck, also can the in the situation that of battery of electric vehicle group fixed voltage, when accelerating and climb, can promote the large electric current that can bear, and promotes the power of power truck.
Under the high situation of electric vehicle lithium battery cost, the cycle life that another current research emphasis is lithium cell, extending battery life can be shared the use cost of lithium cell.Fig. 4 is continuously tested cycle life survey sheet under fixing discharging current, and described measurement is under the most evil bad test condition of having a rest in free of discontinuities, first to discharge and recharge with 1.3C after three circulations of 0.1C activation again.As shown in Figure 4, add electrochemistry Graphene and can obviously increase cycle life.In addition, in specific embodiments of the invention, described electrochemistry Graphene content only accounts for 0.01wt% in integral battery door material, therefore can be expected at and improve after the content of electrochemistry Graphene in integral battery door material, and its cycle life can further significantly promote.
In the specific embodiment of the invention, described lithium cell cathode material is to using the novel matrix material of commercial graphite, a small amount of nano silicon particles and electrochemistry Graphene (Si/ECG) as working electrode.The lithium cell that comprises described negative material be take lithium metal as counter electrode, has electrolytic solution same as the previously described embodiments and barrier film, to make button cell and to carry out electrochemical measurement.In the specific embodiment of the invention, the electrochemistry Graphene of nano silicon particles blending 0.9wt% that described lithium cell cathode material comprises about 0.9wt% and the graphite of 88wt% are as electroactive substance.Table 1 is the part by weight of each material of the embodiment of the present invention.
Table 1
The present invention also provides the comparative example of lithium cell cathode material, assistant director of a film or play's agent of the commercial graphite cathode material that described anode material comprises 92wt%, the tackiness agent of 8wt% and 2wt%, and in solvent NMP intimate mixing, the solid content of gained slurry is controlled at approximately 40% to 50%, is coated with subsequently and rolls to make button cell and carry out electrochemical measurement.
For chemical property relatively, the emphasis of described electrochemical measurement and method be with constant current under different charge-discharge velocities, setting its voltage range is that 0.005V carries out charge-discharge test to 2.5V.
Fig. 5 is commercial graphite cathode charging and discharging curve figure, its commercial negative material that shows comparative example discharges and recharges figure under low current density, wherein first lap cycle life reversible capacitance amount can reach about 255mAh/g, the irreversible loss of capacitance rate of first lap cycle life is approximately 10%, it discharges and recharges the current density that condition is 10mA/g, the charging/discharging voltage of 2.5V to 0.005V.
Fig. 6 is the hybrid composite charging and discharging curve figure having lower than 1% silicon and electrochemistry Graphene and commercial Graphite Electrodes, wherein first lap cycle life reversible capacitance amount is 360mAh/g, the irreversible loss of capacitance rate of first lap cycle life is approximately 10%, it discharges and recharges the current density that condition is 10mA/g, the charging/discharging voltage of 2.5V to 0.005V.Fig. 6 is presented at the negative material of the present invention adding after nano silicon particles and electrochemistry Graphene, and electrical capacity can increase 100mAh/g and reach 360mAh/g than comparative example.Add silicon in negative material of the present invention after, its electrochemistry irreversible reaction does not increase and still maintains 10%.Can infer that thus electrochemistry Graphene can reduce its cubical expansivity in silicium cathode material.Electrochemistry Graphene and silicon have following function in negative material of the present invention: 1) silicon can increase the electrical capacity of negative pole; 2) utilize electrochemistry graphene coated or interlayer silicon, can reduce the cubical expansivity of silicon 400%; 3) adopt the silicon of form of nanoparticles can reduce silicon volumetric expansion.
Fig. 7 is presented under different discharge rates to Fig. 9, the comparison of ECG/Si anode material and its electrical capacity sustainment rate of commercial graphite.Fig. 7 and Fig. 9 show that graphite itself cannot bear compared with high current charge-discharge, and its electrical capacity cannot be recovered after heavy-current discharge, and it represents that inside has produced irreversible reaction.According to anode material of the present invention, add a small amount of ECG/Si and can make its electrical capacity increase, and its first lap is irreversible not because the high cubical expansivity of silicon increases.In addition, Fig. 8 is also presented at after heavy-current discharge, and anode material electrical capacity according to the present invention still can be recovered.The foregoing is only illustrative, but not be restrictive.Any equivalent modifications of without departing from the spirit and scope of the present invention the present invention being carried out or change, all should be contained in appending claims.
Claims (24)
1. an electrochemistry Graphene, it has oxygen level, more than 90% penetration and the sheet resistance below 10k Ω/sq below 20wt%, and wherein said sheet resistance is to take the thickness of electrochemistry Graphene to arrive 5nm as 1.5nm.
2. an electrochemistry Graphene, it is to be made by following steps:
The first electrode and the second electrode are set in electrolytic solution, described the first electrode is graphite material, and described electrolytic solution comprises the ion as insert;
Under the first bias voltage, carry out the embedding step of described graphite material;
Under the second bias voltage, carry out the strip step of described graphite material; And
Take out the Graphene solid in described electrolytic solution.
3. electrochemistry Graphene according to claim 1 and 2, it can pass through following process or upgrading.
4. electrochemistry Graphene according to claim 1 and 2, described processing or upgrading are described electrochemistry Graphene is adulterated or mix nitrogen or other non-carbon with physics or chemical process.
5. according to a purposes for the electrochemistry Graphene described in arbitrary claim in claim 1 to 4, it is for the preparation of lithium cell.
6. a lithium cell, it comprises according to the electrochemistry Graphene described in arbitrary claim in claim 1 to 4 and electrode materials or electrode material precursor.
7. lithium cell according to claim 6, wherein in the amount of described electrode materials or electrode material precursor, described electrochemistry Graphene is to exist to the amount of 5wt% with about 0.001wt%.
8. lithium cell according to claim 6, wherein said electrode materials or electrode material precursor comprise positive electrode material, and described positive electrode material is to be selected from (the LiFe of lithium iron system
(1-x)m
xp
(1-x)o
2 (2-x), 0≤X<1), lithium-cobalt system (LiCoO
2), (LiMn of lithium manganese system
2o
4), (LiNiO of lithium nickel system
2), lithium cobalt manganese nickel three component system (NCM) or its oxide compound or its mixture.
9. lithium cell according to claim 6, wherein said positive electrode material is lithium iron system, lithium iron phosphorus or Lithium Oxide 98min iron phosphorus.
10. lithium cell according to claim 6, wherein said electrode materials or electrode material precursor comprise negative material, and described negative material is to be selected from carbon material, stupalith, silicon (silicon), tin (Tin) and other metal and metal oxide and composition thereof.
11. lithium celies according to claim 6, it further comprises additive.
12. lithium celies according to claim 11, wherein said additive is assistant director of a film or play's agent, tackiness agent, carbon material or solvent.
13. according to the lithium cell described in claim 10 or 12, and wherein said carbon material is carbon fiber or its mixture that is selected from natural and electrographite, soft carbon, hard carbon, carbon nanotube CNT, vapor deposition carbon fiber VGCF, other form.
14. lithium celies according to claim 6, wherein said electrochemistry Graphene and described electrode materials or electrode material precursor carry out mechanically mixing (mechanical mixing), physics or chemical process surfaction (surface modification) or doping (doping).
15. lithium celies according to claim 14, wherein said mechanically mixing is ultrasonic vibration or intimate mixing.
The preparation method of 16. 1 kinds of lithium celies, it comprises the following step:
To carry out mechanically mixing, physics or chemical process surfaction or doping according to the electrochemistry Graphene described in arbitrary claim in claim 1 to 4 and electrode materials or electrode material precursor; And
The product of abovementioned steps gained is carried out to drying-granulating.
17. methods according to claim 16, wherein said mechanically mixing is ultrasonic vibration or intimate mixing.
18. methods according to claim 16, wherein in the amount of described electrode materials or electrode material precursor, described electrochemistry Graphene is to exist to the amount of 5wt% with about 0.001wt%.
19. methods according to claim 16, wherein said drying-granulating step can be heat drying granulation, spray drying granulation or suction filtration drying-granulating.
20. methods according to claim 16, the particle of described drying-granulating step gained is further mixed and made into slurry with additive.
21. methods according to claim 20, wherein said additive is assistant director of a film or play's agent, tackiness agent, carbon material or solvent or its combination.
22. methods according to claim 21, wherein said carbon material is carbon fiber or its mixture that is selected from natural and electrographite, soft carbon, hard carbon, carbon nanotube CNT, vapor deposition carbon fiber VGCF, other form.
23. 1 kinds of electrode composite materials, it comprises graphite, nano silicon particles and according to the electrochemistry Graphene described in arbitrary claim in claim 1 to 4.
24. electrode composite materials according to claim 23, wherein said electrode composite material is anode material.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210254481.XA CN103570002A (en) | 2012-07-20 | 2012-07-20 | Electrochemical graphene and its electrode composites and lithium batteries |
| PCT/US2013/051078 WO2014015139A1 (en) | 2012-07-20 | 2013-07-18 | Graphene-containing electrodes |
| KR1020157003838A KR20150056532A (en) | 2012-07-20 | 2013-07-18 | Graphene-containing electrodes |
| JP2015523253A JP2015527707A (en) | 2012-07-20 | 2013-07-18 | Graphene coated electrode |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210254481.XA CN103570002A (en) | 2012-07-20 | 2012-07-20 | Electrochemical graphene and its electrode composites and lithium batteries |
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| Publication Number | Publication Date |
|---|---|
| CN103570002A true CN103570002A (en) | 2014-02-12 |
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| CN201210254481.XA Pending CN103570002A (en) | 2012-07-20 | 2012-07-20 | Electrochemical graphene and its electrode composites and lithium batteries |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104264179A (en) * | 2014-09-17 | 2015-01-07 | 中国科学院山西煤炭化学研究所 | Method for preparing graphene from raw graphite ores through electrolysis |
| CN106158403A (en) * | 2016-07-15 | 2016-11-23 | 中山大学 | Metal-complexing supermolecule grid and Two-dimensional Carbon composite and preparation method and application |
| CN106315542A (en) * | 2015-06-24 | 2017-01-11 | Bgt材料有限公司 | High-yield single-layered graphene and manufacture method thereof |
| CN107170586A (en) * | 2017-05-10 | 2017-09-15 | 中山大学 | Metal-complexing oversubscription sub-grid and three-dimensional grapheme block composite material, preparation method, purposes and super capacitor electrode |
| CN114497493A (en) * | 2022-01-21 | 2022-05-13 | 华中科技大学 | Electro-exfoliated graphene silicon carbon composite material and its preparation method and application |
| CN115124025A (en) * | 2022-08-16 | 2022-09-30 | 中国石油大学(华东) | A kind of hard carbon material, its preparation method and application in sodium ion battery |
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| CN101562248A (en) * | 2009-06-03 | 2009-10-21 | 龚思源 | Graphite composite lithium ion battery anode material lithium iron phosphate and preparation method thereof |
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Cited By (9)
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| CN104264179A (en) * | 2014-09-17 | 2015-01-07 | 中国科学院山西煤炭化学研究所 | Method for preparing graphene from raw graphite ores through electrolysis |
| CN104264179B (en) * | 2014-09-17 | 2016-06-22 | 中国科学院山西煤炭化学研究所 | A kind of method being prepared Graphene by graphite raw ore electrolysis |
| CN106315542A (en) * | 2015-06-24 | 2017-01-11 | Bgt材料有限公司 | High-yield single-layered graphene and manufacture method thereof |
| CN106158403A (en) * | 2016-07-15 | 2016-11-23 | 中山大学 | Metal-complexing supermolecule grid and Two-dimensional Carbon composite and preparation method and application |
| CN107170586A (en) * | 2017-05-10 | 2017-09-15 | 中山大学 | Metal-complexing oversubscription sub-grid and three-dimensional grapheme block composite material, preparation method, purposes and super capacitor electrode |
| CN107170586B (en) * | 2017-05-10 | 2019-03-29 | 中山大学 | Metal coordination supramolecule grid and three-dimensional grapheme block composite material, preparation method, purposes and super capacitor electrode |
| CN114497493A (en) * | 2022-01-21 | 2022-05-13 | 华中科技大学 | Electro-exfoliated graphene silicon carbon composite material and its preparation method and application |
| CN115124025A (en) * | 2022-08-16 | 2022-09-30 | 中国石油大学(华东) | A kind of hard carbon material, its preparation method and application in sodium ion battery |
| CN115124025B (en) * | 2022-08-16 | 2023-07-21 | 中国石油大学(华东) | A kind of hard carbon material and preparation method thereof and application in sodium-ion battery |
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