CN102569725B - Fluorination grapheme-lithium vanadium phosphate composite material, as well as preparation method and application thereof - Google Patents
Fluorination grapheme-lithium vanadium phosphate composite material, as well as preparation method and application thereof Download PDFInfo
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- CN102569725B CN102569725B CN201010591507.0A CN201010591507A CN102569725B CN 102569725 B CN102569725 B CN 102569725B CN 201010591507 A CN201010591507 A CN 201010591507A CN 102569725 B CN102569725 B CN 102569725B
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Abstract
The invention discloses a fluorination grapheme-lithium vanadium phosphate composite material, as well as the preparation method and the application thereof. The preparation method for the fluorination grapheme-lithium vanadium phosphate composite material comprises the steps as follows: obtaining grapheme; mixing the grapheme with vanadic oxide, villiaumite, phosphate and lithium to form a mixture; calcining and cooling the mixture in the oxygen-free environment to obtain the fluorination grapheme-lithium vanadium phosphate composite material. The preparation method for the fluorination grapheme-lithium vanadium phosphate composite material has a simple technology, is low in cost and contamination-free, and is suitable for industrialized production. The fluorination grapheme-lithium vanadium phosphate composite material prepared through adopting the method has stable structural performance and high electric conductivity, and has high power density when applied for preparing a lithium ion battery or/and anode material of a capacitor.
Description
Technical field
The invention belongs to technical field of inorganic chemical industry, relate to specifically a kind of fluorinated graphene-fluorophosphoric acid vanadium lithium composite material and preparation method thereof and application.
Background technology
Since the strong K sea nurse of the peace moral of Univ Manchester UK (Andre K.Geim) etc. was prepared grapheme material in 2004.Because being subject to people, its unique structure and photoelectric property pay attention to widely.Mono-layer graphite is due to its large specific area, good conduction, heat conductivility and low thermal coefficient of expansion and be considered to desirable material.As: 1, high strength, Young mole, (1,100GPa), fracture strength: (125GPa); 2, high heat conductance, (5,000W/mK); 3, high conductivity, carrier transport rate, (200,000cm
2/ V*s); 4, high specific area, (calculated value: 2,630m
2/ g).Especially the structural property of the nanoscale of its high conductivity matter, large specific surface character and its monolayer two dimension, can be widely used in electrode material.
Fluorographite, as the active material of high-performance lithium ion battery, has caused mechanism of new electrochemical power sources researchers' very big interest and attention, and has succeeded in developing corresponding high-energy battery.Fluorographite-lithium battery has plurality of advantages, as voltage, energy density is high, utilance is high, voltage is steady etc.But also come with some shortcomings, as fluorinated graphite material conductance and stability low, thereby cause battery high-rate performance poor wait not enough.
Summary of the invention
The object of the embodiment of the present invention is to overcome the above-mentioned deficiency of prior art, provides a kind of technique simple, with low cost, is applicable to fluorinated graphene-fluorophosphoric acid vanadium lithium composite material and preparation method thereof of suitability for industrialized production.
And, the fluorinated graphene-fluorophosphoric acid vanadium lithium composite material that a kind of conductivity is high, power density is large, structural behaviour is stable being prepared by said method.
Another object of the embodiment of the present invention be to provide above-mentioned fluorinated graphene-fluorophosphoric acid vanadium lithium composite material as lithium ion battery or/and the application of the positive electrode in capacitor.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
A kind of fluorinated graphene-fluorophosphoric acid vanadium lithium composite material and preparation method thereof, comprises the steps:
Obtain Graphene;
Described Graphene is mixed with vanadic oxide, villiaumite, phosphate, lithium salts, form mixture;
Described mixture is calcined in oxygen-free environment, cooling, obtain described fluorinated graphene-fluorophosphoric acid vanadium lithium composite material.
And, a kind of fluorinated graphene-fluorophosphoric acid vanadium lithium composite material, this material is prepared from by said method.
Further, fluorinated graphene-fluorophosphoric acid vanadium lithium composite material of the present invention as lithium ion battery or/and the application of the positive electrode in capacitor.
Above-mentioned fluorinated graphene-fluorophosphoric acid vanadium lithium composite material and preparation method thereof mixes Graphene, fluorophosphoric acid vanadium lithium and calcines and gets final product to obtain product with villiaumite, its preparation method technique is simple, with low cost, pollution-free, is applicable to suitability for industrialized production.Between the fluorophosphoric acid vanadium lithium containing in the fluorinated graphene-fluorophosphoric acid vanadium lithium composite material being prepared by the method and fluorinated graphene, there is good compatibility, make the stable performance of fluorinated graphene-fluorophosphoric acid vanadium lithium composite structure, wherein, fluorinated graphene has higher conductivity and has the characteristic of fine compatibility with electrolyte, with fluorophosphoric acid vanadium lithium synergy, conductivity performance that fluorinated graphene-fluorophosphoric acid vanadium lithium composite material is high and large power density are given.Use it for and prepare lithium ion battery or/and when the positive electrode of capacitor, lithium ion battery is or/and capacitor power density is large.
Brief description of the drawings
Fig. 1 is fluorinated graphene-fluorophosphoric acid vanadium lithium composite material and preparation method thereof process flow diagram of the embodiment of the present invention;
Fig. 2 contains that to utilize the lithium ion battery of positive plate prepared by fluorinated graphene-fluorophosphoric acid vanadium lithium composite material that the embodiment of the present invention 1 makes be 2.5～5.0V in voltage range, and electric current is the first charge-discharge curve chart under the condition of 1C (156mA/g).
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The embodiment of the present invention provides a kind of technique simple, with low cost, is applicable to fluorinated graphene-fluorophosphoric acid vanadium lithium composite material and preparation method thereof of suitability for industrialized production.This fluorinated graphene-fluorophosphoric acid vanadium lithium composite material and preparation method thereof technological process refers to Fig. 1, and the method comprises the steps:
S1: obtain Graphene;
S2: described Graphene is mixed with vanadic oxide, villiaumite, phosphate, lithium salts, form mixture;
S3: described mixture is calcined in oxygen-free environment, cooling, obtain described fluorinated graphene-fluorophosphoric acid vanadium lithium composite material.
Particularly, in the S1 step of above-mentioned fluorinated graphene-fluorophosphoric acid vanadium lithium composite material and preparation method thereof, Graphene acquisition methods is preferably as follows:
SA1: the preparation of graphene oxide: for graphene oxide, concrete preparation method is referring to the preparation method of the graphene oxide in embodiment 1 by improved Hummers legal system;
SA2: the preparation of Graphene: be mixed with solution by preparing graphene oxide in SA1 step, and vibration carry out individual layer lift-off processing, then add reducing agent at 20～150 DEG C, to carry out reduction reaction 24～48h, Separation of Solid and Liquid, washing, dry, obtain described Graphene.
In above-mentioned SA2 step, the mode of vibration is preferably the mode of sonic oscillation.Reducing agent is preferably hydrazine hydrate, ethylenediamine, NaBH
4in at least one.Product after reduction reaction is carried out to Separation of Solid and Liquid and can adopt filtration or the centrifugal Separation of Solid and Liquid that realizes, can certainly adopt other modes of other this areas to carry out Separation of Solid and Liquid, after Separation of Solid and Liquid, collect solid.Mode to solids wash preferably first washes with water, then washs with alcohol.The object of washing is to remove the foreign material such as the ion that is mingled in solid.Wherein, alcohol particular methanol.
In the S2 step of above-mentioned fluorinated graphene-fluorophosphoric acid vanadium lithium composite material and preparation method thereof, vanadic oxide, phosphate, lithium salts are preferably according to LiVPO
4element chemistry in F measures than carrying out batch mixing, and the mass ratio of villiaumite and Graphene is preferably 1～100: 1, and Graphene and fluorophosphoric acid vanadium lithium (LiVPO
4f) mass ratio is preferably 1～99: 1.Further, the mass ratio of this villiaumite and Graphene is preferably 10: 1, Graphene and fluorophosphoric acid vanadium lithium (LiVPO
4f) mass ratio is preferably 10: 1.This preferred proportioning component, can further improve Stability Analysis of Structures performance, conductivity and the power density of fluorinated graphene-fluorophosphoric acid vanadium lithium composite material.Wherein, villiaumite is preferably at least one in ammonium fluoride, Kynoar, KF, NaF; Lithium salts is preferably at least one in lithium acetate, lithium carbonate, lithium hydroxide; Phosphate is preferably at least one in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate.
In the S3 step of above-mentioned fluorinated graphene-fluorophosphoric acid vanadium lithium composite material and preparation method thereof, oxygen-free environment is preferably the oxygen-free environment that is full of inert gas.This inert gas can be conventional inert gas, as Ar etc.Oxygen-free environment can be also the oxygen-free environment of vacuum state.The temperature of mixture calcining is preferably to 400～800 DEG C, and the time is 2～24h, and further, the temperature of mixture calcining is preferably 500～700, and the time is preferably 7～15h.
Above-mentioned fluorinated graphene-fluorophosphoric acid vanadium lithium composite material and preparation method thereof mixes Graphene, fluorophosphoric acid vanadium lithium and calcines and gets final product to obtain product with villiaumite, its preparation method technique is simple, with low cost, pollution-free, is applicable to suitability for industrialized production.
The embodiment of the present invention also provides a kind of fluorinated graphene-fluorophosphoric acid vanadium lithium composite material, and this fluorinated graphene-fluorophosphoric acid vanadium lithium composite material is by prepared the forming of above-mentioned fluorinated graphene-fluorophosphoric acid vanadium lithium composite material and preparation method thereof.Between the fluorophosphoric acid vanadium lithium containing in the fluorinated graphene-fluorophosphoric acid vanadium lithium composite material being prepared by said method and fluorinated graphene, there is good compatibility, make the stable performance of fluorinated graphene-fluorophosphoric acid vanadium lithium composite structure, wherein, fluorinated graphene has higher conductivity and has the characteristic of fine compatibility with electrolyte, with fluorophosphoric acid vanadium lithium synergy, conductivity performance that fluorinated graphene-fluorophosphoric acid vanadium lithium composite material is high and large power density are given.
There is above-mentioned premium properties just because of above-mentioned fluorinated graphene and fluorophosphoric acid vanadium lithium material, therefore, the embodiment of the present invention further also provide above-mentioned fluorinated graphene-fluorophosphoric acid vanadium lithium composite material as lithium ion battery or/and the application of the positive electrode in capacitor.By this fluorinated graphene-fluorophosphoric acid vanadium lithium composite material for the preparation of lithium ion battery or/and when positive electrode in capacitor, lithium ion battery is or/and capacitor power density is large.
Illustrate below difference composition of fluorinated graphene-fluorophosphoric acid vanadium lithium composite material and preparation method thereof by multiple embodiment, with and the aspect such as performance.
Embodiment 1
The preparation of fluorinated graphene-fluorophosphoric acid vanadium lithium composite material, its method technological process is as follows:
S11: the preparation of Graphene: by improved Hummers legal system for Graphene;
S111: graphite oxide: by improved Hummers legal system for graphene oxide, its concrete steps are: by 20g graphite powder (50 order), 10g potassium peroxydisulfate and 10g phosphorus pentoxide join in the concentrated sulfuric acid of 80 DEG C, stir, more than cooling 6h, refilter, washing is to neutral, dry, and dried sample is added to 0 DEG C, in the concentrated sulfuric acid of 230ml, then add 60g potassium permanganate, and temperature is remained on below 20 DEG C, then in the oil bath of 35 DEG C, keep after 2h, slowly add 920ml deionized water, after 15min, continue to add 2.8L deionized water (wherein contain 50ml concentration be 30% hydrogen peroxide), mixture color becomes glassy yellow afterwards, suction filtration while hot, finally wash with the hydrochloric acid that 5L concentration is 10%, suction filtration, for subsequent use,
S112: the preparation of Graphene: graphene oxide 100mg prepared by S11 step and deionized water 100ml join in the round-bottomed flask of 250ml, the suspension-turbid liquid that now solution is brown color, again suspension-turbid liquid is disperseed with the ultrasonic echography of 150W, then add wherein hydrazine hydrate (1ml, 98%) and be heated to 100 DEG C of reaction 24-48h, then filter, and water 300ml and methyl alcohol 300ml washing successively, at 80 DEG C, dry 48h in vacuum drying chamber, obtains Graphene;
S12: the preparation of fluorinated graphene and fluorophosphoric acid vanadium lithium composite material: the V that gets 0.1mol
2o
5powder, the LiAC of 0.2mol, the NH of 0.2mol
4h
2pO
4, the Graphene of 10g and the NH of 17.4g
4after F mixes, under the condition of argon gas inert gas shielding, 700 DEG C calcining 10h, naturally cooling after, obtain fluorinated graphene-fluorophosphoric acid vanadium lithium composite material.
Fluorinated graphene-fluorophosphoric acid vanadium lithium composite material prepared by the present embodiment is for the preparation of positive plate, and preparation method is as follows:
The preparation of pole piece: take fluorinated graphene-fluorophosphoric acid vanadium lithium composite material 4.5g, acetylene black 0.25g, PVDF0.25g, dripping NMP makes said mixture become pulpous state, fully stirring is coated on metal aluminum foil after making it to mix, coating thickness is 200 μ m, then after 100 DEG C of dry 12h of vacuum, take out, form described pole piece;
Roll-in: pole piece is carried out to roll extrusion with roller mill, and the thickness after roll-in is 165 μ m;
Cut-parts: the pole piece of roll-in is broken into the circular pole piece that diameter is 10mm with card punch, accurately weigh;
The assembling of lithium ion battery: by pole piece, barrier film and electrolyte are assembled into ultracapacitor according to cell making process in glove box, its septation is celgard2000, the LiPF of 1mol/L
6ethylene carbonate (EC) and the mixed liquor of dimethyl carbonate (DMC) (volume ratio 1: 1) be electrolyte, assembled rear leave standstill one day.
Performance Detection: be 2.5～5.0V in voltage range by the lithium ion battery that contains positive plate prepared by fluorinated graphene-fluorophosphoric acid vanadium lithium composite material that the present embodiment 1 makes, electric current is under the condition of 1C (156mA/g), to carry out first constant current charge-discharge after tested, its test result is shown in Fig. 2.As shown in Figure 2, fluorinated graphene-fluorophosphoric acid vanadium lithium composite material prepares that the lithium ion battery power density of positive plate is large, current constant.This charging and discharging curve, near 4.2V, has a charge and discharge platform stably, and under the condition of 1C (156mA/g), discharge capacity is 141mAh/g, illustrates that the present embodiment fluorinated graphene-fluorophosphoric acid vanadium lithium composite material fixture has preferably large high rate performance.
Embodiment 2
The preparation of fluorinated graphene-fluorophosphoric acid vanadium lithium composite material, its method technological process is as follows:
S21: the preparation of Graphene: by improved Hummers legal system for Graphene;
S211: graphite oxide: referring to the S111 step in embodiment 1;
S212: the preparation of Graphene: graphene oxide 100mg prepared by S21 step and deionized water 100ml join in the round-bottomed flask of 250ml, the suspension-turbid liquid that now solution is brown color, again suspension-turbid liquid is disperseed with the ultrasonic echography of 150W, then add wherein ethylenediamine (1ml, 98%) and be heated to 100 DEG C of reaction 24-48h, then filter, and water 300ml and methyl alcohol 300ml washing successively, at 80 DEG C, dry 48h in vacuum drying chamber, obtains Graphene;
S22: the preparation of fluorinated graphene and fluorophosphoric acid vanadium lithium composite material: the V that gets 0.095mol
2o
5powder, the LiAC of 0.2mol, the NH of 0.2mol
4h
2pO
4, after the Graphene of 20g and the KF of 18g mix, under the condition of argon gas inert gas shielding, 600 DEG C calcining 20h, naturally cooling after, obtain fluorinated graphene-fluorophosphoric acid vanadium lithium composite material.
Fluorinated graphene-fluorophosphoric acid vanadium lithium composite material that the present embodiment is made is for the preparation of positive plate.The steps such as this positive plate preparation method comprises preparation, roll-in, the cut-parts of pole piece, the assembling of its concrete preparation process and the lithium ion battery that contains this positive plate refer to embodiment 1.Lithium ion battery test result prepared by this performance of lithium ion battery testing result and embodiment 1 is similar.
Embodiment 3
The preparation of fluorinated graphene-fluorophosphoric acid vanadium lithium composite material, its method technological process is as follows:
S11: the preparation of Graphene: by improved Hummers legal system for Graphene;
S111: graphite oxide: by improved Hummers legal system for graphene oxide, its concrete steps are: by 20g graphite powder (50 order), 10g potassium peroxydisulfate and 10g phosphorus pentoxide join in the concentrated sulfuric acid of 80 DEG C, stir, more than cooling 6h, refilter, washing is to neutral, dry, and dried sample is added to 0 DEG C, in the concentrated sulfuric acid of 230ml, then add 60g potassium permanganate, and temperature is remained on below 20 DEG C, then in the oil bath of 35 DEG C, keep after 2h, slowly add 920ml deionized water, after 15min, continue to add 2.8L deionized water (wherein contain 50ml concentration be 30% hydrogen peroxide), mixture color becomes glassy yellow afterwards, suction filtration while hot, finally wash with the hydrochloric acid that 5L concentration is 10%, suction filtration, for subsequent use,
S112: the preparation of Graphene: graphene oxide 100mg prepared by S11 step and deionized water 100ml join in the round-bottomed flask of 250ml, the suspension-turbid liquid that now solution is brown color, again suspension-turbid liquid is disperseed with the ultrasonic echography of 150W, then add wherein NaBH
4(1ml, 98%) is also heated to 150 DEG C of reaction 24-48h, then filter, and water 300ml and methyl alcohol 300ml washing successively, at 80 DEG C, dry 48h in vacuum drying chamber, obtains Graphene;
S12: the preparation of fluorinated graphene and fluorophosphoric acid vanadium lithium composite material: according to LiVPO
4element chemistry in F measures than taking V
2o
5, lithium carbonate, ammonium phosphate, wherein, V
2o
5powder 0.1mol, and after the Graphene of 20g and the Kynoar of 20g mix, under the condition of nitrogen protection, 800 DEG C of calcining 2h, naturally cooling after, obtain fluorinated graphene-fluorophosphoric acid vanadium lithium composite material.
Embodiment 4
The preparation of fluorinated graphene-fluorophosphoric acid vanadium lithium composite material, its method technological process is as follows:
S11: the preparation of Graphene: by improved Hummers legal system for Graphene;
S111: graphite oxide: by improved Hummers legal system for graphene oxide, its concrete steps are: by 20g graphite powder (50 order), 10g potassium peroxydisulfate and 10g phosphorus pentoxide join in the concentrated sulfuric acid of 80 DEG C, stir, more than cooling 6h, refilter, washing is to neutral, dry, and dried sample is added to 0 DEG C, in the concentrated sulfuric acid of 230ml, then add 60g potassium permanganate, and temperature is remained on below 20 DEG C, then in the oil bath of 35 DEG C, keep after 2h, slowly add 920ml deionized water, after 15min, continue to add 2.8L deionized water (wherein contain 50ml concentration be 30% hydrogen peroxide), mixture color becomes glassy yellow afterwards, suction filtration while hot, finally wash with the hydrochloric acid that 5L concentration is 10%, suction filtration, for subsequent use,
S112: the preparation of Graphene: graphene oxide 100mg prepared by S11 step and deionized water 100ml join in the round-bottomed flask of 250ml, the suspension-turbid liquid that now solution is brown color, again suspension-turbid liquid is disperseed with the ultrasonic echography of 150W, then add wherein NaBH
4(1ml, 98%) is also heated to 150 DEG C of reaction 24-48h, then filter, and water 300ml and methyl alcohol 300ml washing successively, at 80 DEG C, dry 48h in vacuum drying chamber, obtains Graphene;
S12: the preparation of fluorinated graphene and fluorophosphoric acid vanadium lithium composite material: according to LiVPO
4element chemistry in F measures than taking V
2o
5, lithium hydroxide, diammonium hydrogen phosphate mix, wherein, V
2o
5powder 0.1mol, and after the Graphene of 20g and the NaF of 200g mix, under the condition of nitrogen protection, 400 DEG C of calcining 24h, naturally cooling after, obtain fluorinated graphene-fluorophosphoric acid vanadium lithium composite material.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (8)
1. fluorinated graphene-fluorophosphoric acid vanadium lithium composite material and preparation method thereof, comprises the steps:
Obtain Graphene;
Described Graphene is mixed with vanadic oxide, villiaumite, phosphate, lithium salts, form mixture;
Wherein, described vanadic oxide, phosphate, lithium salts are according to LiVPO
4in F, element chemistry measures than mixing, and the mass ratio of described villiaumite and Graphene is 1～100:1, and the mass ratio of described Graphene and fluorophosphoric acid vanadium lithium is 1～99:1; Described villiaumite is at least one in ammonium fluoride, Kynoar, KF, NaF;
Described mixture is calcined in oxygen-free environment, cooling, obtain described fluorinated graphene-fluorophosphoric acid vanadium lithium composite material.
2. fluorinated graphene-fluorophosphoric acid vanadium lithium composite material and preparation method thereof according to claim 1, is characterized in that: the mass ratio of described villiaumite and Graphene is 10:1, the mass ratio of described Graphene and fluorophosphoric acid vanadium lithium is 10:1.
3. according to the arbitrary described fluorinated graphene-fluorophosphoric acid vanadium lithium composite material and preparation method thereof of claim 1～2, it is characterized in that:
Lithium salts is at least one in lithium acetate, lithium carbonate, lithium hydroxide;
Phosphate is at least one in ammonium dihydrogen phosphate, ammonium phosphate, diammonium hydrogen phosphate.
4. fluorinated graphene-fluorophosphoric acid vanadium lithium composite material and preparation method thereof according to claim 1, is characterized in that: the temperature of described calcining is 400～800 DEG C, the time is 2～24h.
5. fluorinated graphene-fluorophosphoric acid vanadium lithium composite material and preparation method thereof according to claim 1, is characterized in that: described oxygen-free environment is the oxygen-free environment that is full of inert gas.
6. fluorinated graphene-fluorophosphoric acid vanadium lithium composite material and preparation method thereof according to claim 1, is characterized in that: described in obtain Graphene and comprise the steps:
Produce graphene oxide;
Described graphene oxide is mixed with to solution, carries out individual layer lift-off processing by vibration, then add reducing agent at 20～150 DEG C, to carry out reduction reaction 24～48h, filter, washing, dry, obtain described Graphene.
7. fluorinated graphene-fluorophosphoric acid vanadium lithium composite material and preparation method thereof according to claim 6, is characterized in that: described reducing agent is hydrazine hydrate, ethylenediamine, NaBH
4in at least one.
8. fluorinated graphene-fluorophosphoric acid vanadium lithium composite material, is characterized in that: described fluorinated graphene-fluorophosphoric acid vanadium lithium composite material is to be prepared from according to the arbitrary described fluorinated graphene-fluorophosphoric acid vanadium lithium composite material and preparation method thereof of claim 1～7.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107799754A (en) * | 2017-10-31 | 2018-03-13 | 湖南国盛石墨科技有限公司 | A kind of preparation method of fluorophosphoric acid vanadium lithium/fluorinated graphene composite positive pole |
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| CN104009227B (en) * | 2014-05-16 | 2016-06-22 | 齐鲁工业大学 | A kind of LiVPO4The preparation method of F/ nano-pore graphene lithium ion battery positive pole material |
| CN104577120B (en) * | 2015-01-04 | 2016-09-14 | 合肥国轩高科动力能源有限公司 | Phosphoric acid vanadium lithium and the preparation method of fluorinated phosphate vanadium lithium composite positive pole |
| CN104993145A (en) * | 2015-05-29 | 2015-10-21 | 深圳好电科技有限公司 | Electrode with fluorinated graphene as conductive agent and application in lithium ion batteries |
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| CN109671910A (en) * | 2018-12-20 | 2019-04-23 | 漳州旗滨玻璃有限公司 | The preparation method of positive conductive electrode, battery and battery |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101290986A (en) * | 2007-04-18 | 2008-10-22 | 深圳市比克电池有限公司 | Preparing method of Li*V*(PO*)*/C positive pole and prepared positive pole material |
| CN101857221A (en) * | 2010-05-21 | 2010-10-13 | 哈尔滨工业大学 | Method for preparing graphene compounds and graphene oxide compounds with high efficiency |
| CN101877405A (en) * | 2010-04-20 | 2010-11-03 | 华南理工大学 | Preparation method of lithium titanate-graphene combination electrode material |
| CN101882480A (en) * | 2010-06-18 | 2010-11-10 | 中国科学院电工研究所 | Preparation method of polypyrrole/ graphene composite material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101320808A (en) * | 2008-07-14 | 2008-12-10 | 桂林工学院 | Method for preparing lithium ion battery anode material vanadium lithium fluophosphate by one-step solid phase reaction |
-
2010
- 2010-12-16 CN CN201010591507.0A patent/CN102569725B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101290986A (en) * | 2007-04-18 | 2008-10-22 | 深圳市比克电池有限公司 | Preparing method of Li*V*(PO*)*/C positive pole and prepared positive pole material |
| CN101877405A (en) * | 2010-04-20 | 2010-11-03 | 华南理工大学 | Preparation method of lithium titanate-graphene combination electrode material |
| CN101857221A (en) * | 2010-05-21 | 2010-10-13 | 哈尔滨工业大学 | Method for preparing graphene compounds and graphene oxide compounds with high efficiency |
| CN101882480A (en) * | 2010-06-18 | 2010-11-10 | 中国科学院电工研究所 | Preparation method of polypyrrole/ graphene composite material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107799754A (en) * | 2017-10-31 | 2018-03-13 | 湖南国盛石墨科技有限公司 | A kind of preparation method of fluorophosphoric acid vanadium lithium/fluorinated graphene composite positive pole |
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