CN102593436A - Self-supporting flexible carbon nano-tube paper composite electrode material for lithium ion battery - Google Patents
Self-supporting flexible carbon nano-tube paper composite electrode material for lithium ion battery Download PDFInfo
- Publication number
- CN102593436A CN102593436A CN2012100465902A CN201210046590A CN102593436A CN 102593436 A CN102593436 A CN 102593436A CN 2012100465902 A CN2012100465902 A CN 2012100465902A CN 201210046590 A CN201210046590 A CN 201210046590A CN 102593436 A CN102593436 A CN 102593436A
- Authority
- CN
- China
- Prior art keywords
- cnt
- electrode material
- carbon nano
- lithium ion
- ion battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a self-supporting flexible carbon nano-tube paper composite electrode material for a lithium ion battery. A carbon nano-tube paper network of the material is formed by using interlaced carbon nano-tubes, and active anode material particles or cathode material particles of the lithium ion battery are compounded with carbon nano-tube paper to form the carbon nano-tube paper composite electrode material. In the electrode material, the carbon nano-tubes form an efficient three-dimensional conductive network, so that a better electron channel is provided for active material particles with low electrical conductivity. Because a bonding agent and a current collector are not needed, the electrode material has a higher active material ratio, and the performance of the electrode material is further improved. Meanwhile, the high mechanical property of the carbon nano-tube paper makes the composite electrode material show flexible characteristics, and as a flexible electrode material, the self-supporting flexible carbon nano-tube paper composite electrode material is hopeful to be widely used in next-generation flexible electronic equipment.
Description
Invention field
The present invention relates to a kind of electrode material of lithium ion battery, relate in particular to a kind of lithium ion battery, belong to Chemical Engineering and derived energy chemical field with self-supporting flexible carbon nano tube paper combination electrode material.
Background technology
Lithium ion battery is used widely in personal electronic equipments as one type of battery with high energy density at present.Yet; Continuous leap along with the personal portable device performance; Its requirement to supporting energy resource system also improves constantly; Need exploitation to have high-energy more, more high power density, more long-life even lithium ion battery, so that be fit to the lithium ion battery of electronic equipment of future generation with characteristics such as flexibilities.
Lithium ion battery moves storage and the release that realizes electric energy between the positive and negative polarities active material through lithium ion.This energy storage mechanism has determined the active material at the two poles of the earth to set up than good electron and ion channel.In lithium battery, be mostly graininess at present, and have lower intrinsic conductivity mostly, influenced the actual performance of electrode material by the both positive and negative polarity active material that extensively adopts.With the positive electrode particle is example, LiCoO
2, LiMn
2O
4, LiFePO
4, LiMnPO
4, Li
3V
2(PO
4)
3And LiNi
0.5Mn
1.5O
4All be graininess Deng anode active material of lithium ion battery; In being processed as the process of electrodes of lithium-ion batteries; Need with conductive additive (conductive carbon black etc.), binding agent (Kynoar etc.), mix to form slurry and also be coated in respective episode fluid (aluminium foil etc.) and go up and form pole piece.It should be noted that mostly the binding agent in the pole piece is macromolecular material, can reduce the whole conductivity of material, also can influence the pore passage structure of pole piece simultaneously to a certain extent; The existence of collector also makes the mass fraction of active material in whole pole piece descend, and influences pole piece integral energy density.The anticathode material is like Fe
3O
4, Fe
2O
3, SnO
2, TiO
2, Li
4Ti
5O
12With Si similar process is arranged also.In order further to improve the conductivity of anode pole piece; Existing work is replaced into CNT with above-mentioned conductive additive conductive carbon black; And mix coating with binding agent, the method can further be improved conductivity (Zhang Qingtang, the Qu Meizhen of pole piece to a certain extent; Etc. patent publication No.: CN1770515A), but still need to use binding agent and collector.How to be more excellent electronics and the ion channel of active material structure, and acquisition further raising active material mass ratio in pole piece is to receive question of common concern in this area always.
CNT is as one type of tubular material with superior electrical conductivity.Have benefited from its excellent mechanical performance, long CNT itself can overlap each other and form paper shape structure, need not any conductive agent, and this CNT paper has toughness preferably, has the characteristic of flexible and weak property electric conducting material.Based on this phenomenon, this patent has proposed the lithium ion battery electrode material of a kind of structure based on the CNT paper composites, is skeleton with CNT paper, and the active positive and negative pole material of lithium ion battery is wherein compound.In this electrode, the CNT that interweaves forms good conductive network, and suitable flexible pore passage structure is provided, and makes the active material of battery can bring into play its performance better; The phenomenon that its excellent mechanical performance has also avoided bulk effect causes in the active material charge and discharge process same collector to peel off has improved the cyclical stability of electrode material.Simultaneously, CNT paper combination electrode need not binding agent and collector, itself can be directly uses as pole piece, makes that the active material accounting is corresponding to be improved.Even it should be noted that composite reactive material granule in CNT paper, it still can keep certain flexible characteristic, is a kind of electrode material that can be used for flexible lithium ion battery.
This shows; If can develop a kind of lithium ion battery electrode material based on the CNT paper composites; Then be expected to further promote the chemical property of electrode material; Obtain more excellent energy density, the new feature of electrode materials such as charge-discharge performance and exploitation flexibility promotes the further raising and the development of lithium ion battery level.
Summary of the invention
It is lower to the objective of the invention is to change in the present lithium ion battery electrode material conductive network efficient, and relies on the present situation of binding agent, collector, proposes a kind of combination electrode material based on flexible carbon nano tube paper.Can make full use of conductive network good in the CNT paper, and rely on its mechanical performance to break away from dependence, further improve the performance of overall electrode material binding agent and collector.
Technical scheme of the present invention is following:
A kind of lithium ion battery is characterized in that with self-supporting flexible carbon nano tube paper combination electrode material: this combination electrode material is made up of CNT paper and lithium ion battery active material particle; Wherein CNT paper is the CNT carbon nano-tube macroscopic body that assembling forms that is interweaved; Active material particle is positive electrode particle or negative material particle; Active material particle is embedded in the CNT paper through recombination process, and wherein the mass ratio of CNT and active material particle is between 1: 0.05～50.
CNT caliber in the CNT paper according to the invention is between 1～100 nanometer, and length of carbon nanotube is between 0.5～2000 micron.
Described anode material for lithium-ion batteries particle is LiCoO
2, LiMn
2O
4, LiFePO
4, LiMnPO
4, Li
3V
2(PO
4)
3And LiNi
0.5Mn
1.5O
4In one or several; Said lithium ion battery negative material particle is Fe
3O
4, Fe
2O
3, SnO
2, TiO
2, Li
4Ti
5O
12With among the Si one or more.
Said active material particle size is between the 2-2000 nanometer.
Said 1) recombination process of CNT and active material particle comprises in:
A) mechanical mixture of CNT and active material particle, reprocessing form CNT paper combination electrode material;
B) active material is directly grown on the CNT, and reprocessing forms CNT paper combination electrode material;
C) active material is directly grown in the CNT paper, forms CNT paper combination electrode material.
The present invention compares prior art; Have following advantage and high-lighting effect: the present invention adopts the CNT paper of long CNT structure as the lithium ion battery electrode material skeleton first; Make full use of the conduction and the mechanical performance of CNT; For active material provides good electron and ion channel, the capacitance loss that its characteristics with certain flexibility of while have also avoided the active material change in volume to cause.In addition, the characteristics of this electrode material self-supporting make electrode material be able to avoid the use of binding agent and collector, can improve the phase answer seizure ratio of active material in the electrode material.The appearance of this material can be from the energy density of electrode material, and aspects such as power-performance and flexible characteristic improve the performance of lithium ion battery electrode material, help to advance the progress and the development of lithium ion battery industry.
Description of drawings
The scanning electron microscope diagram in Fig. 1 CNT paper combination electrode cross section.
The film long cycle performance comparison diagram of electrode of Fig. 2 CNT paper combination electrode and conventional carbon nanotube.
Embodiment
A kind of lithium ion battery with self-supporting flexible carbon nano tube paper combination electrode material by CNT paper as skeleton, the lithium ion battery active electrode material compound with skeleton in form.Wherein CNT prepares through methods such as the chemical vapour deposition (CVD) of swimming, thermal chemical vapor deposition, fluidized-bed chemical vapor depositions; Its CNT caliber is distributed between 1～100 nanometer, and the distribution of lengths of CNT is between 0.5～2000 micron.
The compound of this carbon nano-tube material and lithium ion battery active material realized through following composite pathway:
A) mechanical mixture of CNT and active material particle, reprocessing form CNT paper combination electrode material;
B) active material is directly grown on the CNT, and reprocessing forms CNT paper combination electrode material;
C) active material is directly grown in the CNT paper, forms CNT paper combination electrode material.
Active material comprises that mainly the positive electrode particle is LiCoO
2, LiMn
2O
4, LiFePO
4, LiMnPO
4, Li
3V
2(PO
4)
3And LiNi
0.5Mn
1.5O
4In one or several; Negative material is Fe
3O
4, Fe
2O
3, SnO
2, TiO
2, Li
4Ti
5O
12With among the Si one or more; Active material particle is distributed as 2～2000 nanometers.In final CNT paper combination electrode material, the mass ratio of CNT and active material is 1: 0.05～50.
The one-tenth paper mode of CNT or CNT/active material compound forms solution for being dispersed in the liquid phase, and forms CNT paper through evaporation, filtration or vacuum filtration process.This CNT can independently exist and direct lithium ion battery electrode material as binder free, no collector.Simultaneously, because this CNT paper combination electrode provides good conductive network and pore passage structure preferably, making this electrode body reveal better chemical property, is a kind of self-supporting lithium ion battery electrode material of excellent performance.
Can further understand the present invention from following examples, but the present invention not only is confined to following examples.
Embodiment 1:
With the fluidized-bed chemical vapor deposition process, vermiculite is caliber 10 nanometers of Preparation of Catalyst, and the CNT that length is 50 microns is a raw material; With commercial LiFePO
4(particle diameter is 100 nanometers) is positive electrode active materials assembled carbon nano-tube paper combination electrode material.With CNT and LiFePO4 (LiFePO
4) particle shears and to be scattered in (CNT concentration 1mg/mL, LiFePO in the 100mL N-methyl pyrrolidone
4Granule density 4mg/mL).Method through vacuum filtration obtains CNT paper/LiFePO on filter paper
4Particulate composite can take off CNT paper from filter paper through drying, and this CNT paper combination electrode has pliability preferably, can issue in external force to give birth to than large elastic deformation.The mass ratio of CNT and active material is 1: 4 in the electrode.The LiFePO4 particle is distributed in the CNT gauze network more equably in the cross section of this electrode material of sem observation demonstration, forms the structure (accompanying drawing 1) of self-supporting.Electrochemical results shows that this CNT paper electrode is compared the electrode of traditional handicraft acquisition (by LiFePO
4Particle, carbon nanotube conducting slurry, binding agent, collector constitute), present more excellent long cyclical stability (accompanying drawing 2, discharging and recharging intensity is 1C), and have lower characteristics such as equiva lent impedance.
Embodiment 2:
The CNT that obtains with the chemical vapor deposition processes that swims is a raw material, caliber 100 nanometers, 1000 microns of length; With cobalt oxide and lithium carbonate is raw material, presses Li: Co=1: 1 molar ratio weighing, and be mixed into promoting the circulation of qi stream with CNT and shear and disperse.It is synthetic under 800-900 ℃ of following high temperature, to carry out high temperature solid-state, promptly obtains cobalt acid lithium (LiCoO
2) particle/composite structure of carbon nano tube, LiCoO
2Particle is of a size of 1 micron.Placing the dimethyl formamide liquid phase to shear this carbon nano tube compound material disperses; And method acquisition CNT paper material through filtering; Can this CNT paper combination electrode material be taken off CNT and LiCoO in this combination electrode from filter paper after the oven dry
2The mass ratio of particle is 1: 0.1, presents good mechanical performance, can directly use as electrode, wherein positive electrode particle LiCoO
2After 100 circulations under the strength of discharge of 0.2C, still can keep the capacity of 125mAh/g, present excellent cycle performance.
Embodiment 3:
The CNT that obtains with the thermal chemical vapor deposition process is a raw material, this CNT caliber 1 nanometer, 0.5 micron of length.This CNT is scattered in FeSO through the liquid phase shear history
4In the solution, in pH is about 10 environment, adopt oxygen to induce and air oxidation in succession, the method through the chemical oxidation deposition obtains tri-iron tetroxide (Fe
3O
4)/carbon mano-tube composite; Wherein the particle size of tri-iron tetroxide is 50 nanometers; Obtaining with the tri-iron tetroxide through filtering and washing is the CNT paper combination electrode of negative active core-shell material, and the mass ratio of CNT and tri-iron tetroxide is 1: 10 in this electrode material, and capacity still can keep 400mAh/g after 100 circulations under the strength of discharge of 0.1C; Less than 25%, present excellent cycle performance than the initial capacity decay.
Embodiment 4:
The CNT that obtains with the chemical gaseous phase process of swimming is a raw material, and this CNT caliber is 30 nanometers, and length is 500 microns; CNT is dispersed in the aqueous solution, and adds sucrose, ammonium metavanadate, lithium hydroxide, ammonium dihydrogen phosphate carry out hydro-thermal synthetic (160 ℃, 2 hours).Hydrothermal product through 700 ℃ of calcinings obtain CNT and phosphoric acid vanadium lithium (Li
3V
2(PO
4)
3) compound, the particle size of phosphoric acid vanadium lithium is 500 nanometers in this compound.This compound is placed the aqueous solution, under lower power, carry out ultrasonic dispersion, 60 ℃ of evaporation film forming formation CNT paper combination electrodes are down carried out to solution in the back.The mass ratio of CNT and active material phosphoric acid vanadium lithium is 1: 0.5 in this pole piece.
Embodiment 5:
The CNT that obtains with the thermal chemical vapor deposition process is a raw material, these CNT caliber 20 nanometers, 200 microns of length; CNT is disperseed in the N-methyl pyrrolidone and suction filtration acquisition pure nano-carbon tube paper structure.After the oven dry with this CNT paper as in the quartz tube reactor, be warming up to 750 ℃ and feed silane gas under the inert ambient environment.Silane original position thermal cracking forms silicon (Si) particle in CNT paper, little 10 nanometers of average particle size.Cooling is taken out and promptly is able to the CNT paper combination electrode that nano silicon particles is a negative active core-shell material, and the mass ratio of CNT and nano silicon particles is 1: 50 in this electrode.In charge and discharge process, CNT paper pilotaxitic texture provides the favorable mechanical performance, and the process that breaks away from collector that has limited effectively that change in volume causes in the silicon grain charge and discharge process presents excellent cycle performance.
Embodiment 6:
The CNT that obtains with the thermal chemical vapor deposition process is a raw material, these CNT caliber 5 nanometers, and length is 2000 microns, with CNT and LiMn2O4 (LiMn
2O
4), lithium manganese phosphate (LiMnPO
4) two kinds of particles add dimethyl formamide jointly and disperse, and suction filtration forms CNT paper combination electrode material.LiMn
2O
4, LiMnPO
4Two kinds of particles are of a size of 2000 nanometers, CNT and positive electrode active materials (LiMn in the electrode material
2O
4, LiMnPO
4) mass ratio be 1: 0.2.
Embodiment 7:
The CNT that obtains with the chemical vapor deposition processes that swims is a raw material, these CNT caliber 50 nanometers, and length is 10 microns.With this CNT and nickel LiMn2O4 (LiNi
0.5Mn
1.5O
4) particle (particle diameter 200 nanometers) disperses in the N-methyl pyrrolidone, and the method for passing through to filter obtains CNT paper/nickel LiMn2O4 combination electrode material on filter paper.Dry back obtains self-supporting CNT paper combination electrode, and the mass ratio of CNT and nickel LiMn2O4 is 1: 20 in the combination electrode.
Embodiment 8:
The CNT that on the hydrotalcite type catalyst, obtains with the fluidized-bed chemical vapor deposition process is a raw material, and the average caliber of this CNT is 8 nanometers, and length is 2 microns.This CNT is scattered in the aqueous solution, and the aqueous dispersions and the lithium hydroxide solution that add anatase carry out 180 ℃ of following 12 hours water-heat processes, original position is synthetic to have a lithium titanate particle (Li through having obtained after the washing on CNT
4Ti
5O
12, average diameter 20 nanometers) sample.With this CNT/lithium titanate compound and length is that 500 microns CNT co-dispersed is in the N-methyl pyrrolidone; And suction filtration acquisition CNT paper/lithium titanate composite electrode material, wherein the mass ratio of CNT and lithium titanate active material is 1: 1.Be assembled into that the lithium titanate capacity still remains on about 150mAh/g after test result shows 500 circulations behind the half-cell, present excellent cycle performance.
Embodiment 9:
The CNT that obtains with thermal chemical vapor deposition is a raw material, and the average caliber of this CNT is 3 nanometers, and average length is 100 microns.Place the benzyl alcohol solution liquid phase to shear this CNT and disperse, and add iron oxide (Fe
2O
3) and tin oxide (SnO
2) the common shearing of nano particle (average diameter is respectively 1500 nanometers and 300 nanometers) carry out mechanical mixture.The back obtains CNT/iron oxide/tin oxide combination electrode material through evaporation drying, and the mass ratio of CNT and active material (iron oxide and tin oxide) is 1: 0.05 in this self-supporting CNT paper combination electrode.
Embodiment 10:
The CNT that obtains with the chemical vapor deposition processes that swims is a raw material, and the average caliber of this CNT is 80 nanometers, and average length is 1500 microns.Under nitrogen environment, CNT is scattered in the ethanol, and drips titanium tetrachloride, triethanolamine and ammoniacal liquor, place 145 ℃ of following hydro-thermal ageings 48 hours, take out the washing back and obtain CNT/titanium oxide (TiO
2) composite material, wherein the average grain diameter of titanium oxide is 2 nanometers.This composite material liquid phase in the N-methyl pyrrolidone is sheared dispersion and suction filtration, and obtaining with the titanium oxide is the CNT paper combination electrode material of active material, and wherein the mass ratio of CNT and titanium oxide is 1: 30.
Claims (5)
1. a lithium ion battery is with self-supporting flexible carbon nano tube paper combination electrode material, and it is characterized in that: this combination electrode material is made up of CNT paper and lithium ion battery active material particle; Wherein CNT paper is the CNT carbon nano-tube macroscopic body that assembling forms that is interweaved; Active material particle is positive electrode particle or negative material particle; Active material particle is embedded in the CNT paper through recombination process, and wherein the mass ratio of CNT and active material particle is 1: between the 0.05-50.
According to the described a kind of lithium ion battery of claim 1 with self-supporting flexible carbon nano tube paper combination electrode material; It is characterized in that: the CNT caliber in the said CNT paper is between the 1-100 nanometer, and length of carbon nanotube is between the 0.5-2000 micron.
According to the described a kind of lithium ion battery of claim 1 with self-supporting flexible carbon nano tube paper combination electrode material, it is characterized in that: described anode material for lithium-ion batteries particle is LiCoO
2, LiMn
2O
4, LiFePO
4, LiMnPO
4, Li
3V
2(PO
4)
3And LiNi
0.5Mn
1.5O
4In one or several; Said lithium ion battery negative material particle is Fe
3O
4, Fe
2O
3, SnO
2, TiO
2, Li
4Ti
5O
12With among the Si one or more.
According to the described a kind of lithium ion battery of claim 1 with self-supporting flexible carbon nano tube paper combination electrode material, it is characterized in that: said active material particle size is between the 2-2000 nanometer.
According to the described a kind of lithium ion battery of the arbitrary claim of claim 1～4 with self-supporting flexible carbon nano tube paper combination electrode material, it is characterized in that: several kinds of situation below the recombination process of said CNT and active material particle adopts:
A) after CNT and the active material particle mechanical mixture, reprocessing forms CNT paper combination electrode material;
B) active material is directly grown on the CNT, and reprocessing forms CNT paper combination electrode material;
C) active material is directly grown in the CNT paper, forms CNT paper combination electrode material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100465902A CN102593436A (en) | 2012-02-27 | 2012-02-27 | Self-supporting flexible carbon nano-tube paper composite electrode material for lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100465902A CN102593436A (en) | 2012-02-27 | 2012-02-27 | Self-supporting flexible carbon nano-tube paper composite electrode material for lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102593436A true CN102593436A (en) | 2012-07-18 |
Family
ID=46481801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100465902A Pending CN102593436A (en) | 2012-02-27 | 2012-02-27 | Self-supporting flexible carbon nano-tube paper composite electrode material for lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102593436A (en) |
Cited By (41)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102945947A (en) * | 2012-12-04 | 2013-02-27 | 中国科学院上海硅酸盐研究所 | Preparation method of flexible binding agent-free self-support combination electrode |
| CN103280581A (en) * | 2013-05-20 | 2013-09-04 | 中国科学院过程工程研究所 | Negative material of lithium-ion battery and preparation method of negative material |
| CN103325998A (en) * | 2013-05-15 | 2013-09-25 | 同济大学 | Flexible nano SnO2/Si composite lithium ion battery negative-electrode material and preparation method thereof |
| CN103337632A (en) * | 2013-07-10 | 2013-10-02 | 肖辉 | Carbon nanopaper supported lithium iron phosphate lithium ion positive electrode and making method thereof |
| CN103413927A (en) * | 2013-08-12 | 2013-11-27 | 浙江大学 | Lithium titanate/iron sesquioxide composite lithium ion battery cathode material and preparation method thereof |
| CN103682368A (en) * | 2012-09-20 | 2014-03-26 | 中国科学院金属研究所 | Rapidly charged flexible lithium ion battery and preparation method of electrodes of rapidly charged flexible lithium ion battery |
| CN103682307A (en) * | 2013-11-27 | 2014-03-26 | 山东精工电子科技有限公司 | LiNi0.5Mn1.5O4/lithium titanate battery and preparation method thereof |
| CN103730630A (en) * | 2013-12-25 | 2014-04-16 | 北京大学深圳研究生院 | Combined electrode of battery and preparation method thereof |
| CN103779106A (en) * | 2013-12-31 | 2014-05-07 | 昆明纳太能源科技有限公司 | Nanometer carbon paper for super-capacitor and preparing method thereof |
| CN103904366A (en) * | 2014-03-09 | 2014-07-02 | 复旦大学 | Flexible linear lithium ion battery and preparation method thereof |
| CN104241601A (en) * | 2014-07-02 | 2014-12-24 | 宁波艾特米克锂电科技有限公司 | Preparation method of metal-current-collector-free lithium battery or super-capacitor electrode |
| CN104505498A (en) * | 2014-12-12 | 2015-04-08 | 天津大学 | Preparation method of ferric oxide/carbon nanotube lithium ion battery anode material |
| CN104752731A (en) * | 2013-12-25 | 2015-07-01 | 比亚迪股份有限公司 | Flexible lithium ion battery current collector, flexible lithium ion battery and preparation method of flexible lithium ion battery |
| CN104795540A (en) * | 2015-03-17 | 2015-07-22 | 江苏乐能电池股份有限公司 | Making method of flexibly packaged coiled battery with high specific energy |
| CN105185965A (en) * | 2015-09-23 | 2015-12-23 | 清华大学 | Flexible carbon-sulfur composite cathode material for lithium-sulfur battery |
| CN105551824A (en) * | 2015-12-17 | 2016-05-04 | 上海奥威科技开发有限公司 | Self-support supercapacitor free of metallic current collector |
| CN106374099A (en) * | 2016-11-02 | 2017-02-01 | 哈尔滨工业大学 | Flexible self-supporting lithium-rich manganese-based cathode for lithium ion battery and preparation method thereof |
| CN107394159A (en) * | 2017-07-24 | 2017-11-24 | 江苏大学 | A kind of composite fibre negative material and preparation method thereof |
| CN108122686A (en) * | 2016-11-28 | 2018-06-05 | 中国科学院大连化学物理研究所 | The Li of fluoride cladding4Ti5O12/ carbon nanotubes composite negative pole material and its preparation and application |
| CN108807884A (en) * | 2018-05-31 | 2018-11-13 | 中国科学院过程工程研究所 | A kind of system and method for lithium ion battery negative material carbon coating modification |
| CN108842140A (en) * | 2018-05-31 | 2018-11-20 | 中国科学院过程工程研究所 | A kind of system and method for anode material for lithium-ion batteries coated modified carbon |
| CN108987796A (en) * | 2018-09-10 | 2018-12-11 | 江西克莱威纳米碳材料有限公司 | A kind of flexible lithium ion battery and preparation method thereof |
| CN109273755A (en) * | 2018-09-25 | 2019-01-25 | 福建省致格新能源电池科技有限公司 | A kind of flexibility secondary cell and its component |
| CN109509866A (en) * | 2017-09-15 | 2019-03-22 | 本田技研工业株式会社 | By the method for cell connector attachment structure self-supporting electrode |
| CN109742327A (en) * | 2018-12-29 | 2019-05-10 | 西安鸿钧睿泽新材料科技有限公司 | Preparation method of self-supporting flexible lithium ion battery carbon cloth loaded LiFePO4 positive electrode material |
| CN109755497A (en) * | 2017-11-08 | 2019-05-14 | 株式会社Lg化学 | Electrode with three-dimensional structure and the electrochemical appliance comprising it |
| US10658651B2 (en) | 2017-07-31 | 2020-05-19 | Honda Motor Co., Ltd. | Self standing electrodes and methods for making thereof |
| CN111477871A (en) * | 2019-01-24 | 2020-07-31 | 本田技研工业株式会社 | Method of making free-standing electrodes supported by carbon nanostructured filaments |
| CN111525114A (en) * | 2020-05-09 | 2020-08-11 | 四川聚创石墨烯科技有限公司 | Method for continuously preparing current collector-free silicon-carbon negative electrode paper |
| CN112176771A (en) * | 2020-09-25 | 2021-01-05 | 柔电（武汉）科技有限公司 | Preparation method of lithium-philic carbon nanotube paper and preparation method of composite metal lithium cathode |
| CN112467104A (en) * | 2020-11-23 | 2021-03-09 | 复旦大学 | Preparation method of lithium cobaltate thick electrode |
| US11081684B2 (en) | 2017-05-24 | 2021-08-03 | Honda Motor Co., Ltd. | Production of carbon nanotube modified battery electrode powders via single step dispersion |
| US11171324B2 (en) | 2016-03-15 | 2021-11-09 | Honda Motor Co., Ltd. | System and method of producing a composite product |
| US11201318B2 (en) | 2017-09-15 | 2021-12-14 | Honda Motor Co., Ltd. | Method for battery tab attachment to a self-standing electrode |
| CN113793931A (en) * | 2021-11-18 | 2021-12-14 | 河南电池研究院有限公司 | Iron oxide negative electrode material for lithium ion battery and preparation method thereof |
| US11325833B2 (en) | 2019-03-04 | 2022-05-10 | Honda Motor Co., Ltd. | Composite yarn and method of making a carbon nanotube composite yarn |
| US11352258B2 (en) | 2019-03-04 | 2022-06-07 | Honda Motor Co., Ltd. | Multifunctional conductive wire and method of making |
| US11383213B2 (en) | 2016-03-15 | 2022-07-12 | Honda Motor Co., Ltd. | System and method of producing a composite product |
| CN115403033A (en) * | 2022-10-09 | 2022-11-29 | 清华大学 | Conductive agent for lithium ion battery, negative electrode and preparation method thereof, and lithium ion battery |
| US11539042B2 (en) | 2019-07-19 | 2022-12-27 | Honda Motor Co., Ltd. | Flexible packaging with embedded electrode and method of making |
| US11569490B2 (en) | 2017-07-31 | 2023-01-31 | Honda Motor Co., Ltd. | Continuous production of binder and collector-less self-standing electrodes for Li-ion batteries by using carbon nanotubes as an additive |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008124167A1 (en) * | 2007-04-10 | 2008-10-16 | The Regents Of The University Of California | Charge storage devices containing carbon nanotube films as electrodes and charge collectors |
| CN101315974A (en) * | 2007-06-01 | 2008-12-03 | 清华大学 | Lithium ionic cell cathode and method for producing the same |
| CN101388447A (en) * | 2007-09-14 | 2009-03-18 | 清华大学 | Negative pole for lithium ionic cell and prepraring method thereof |
| CN101420021A (en) * | 2007-10-26 | 2009-04-29 | 清华大学 | Positive pole of lithium ion cell and preparation method thereof |
| CN101582302A (en) * | 2008-05-14 | 2009-11-18 | 清华大学 | Carbon nano tube/conductive polymer composite material |
| US20110256451A1 (en) * | 2009-12-21 | 2011-10-20 | Cui li-feng | Nanotube-based nanomaterial membrane |
| CN102270761A (en) * | 2010-06-03 | 2011-12-07 | 上海空间电源研究所 | Method for making integrated flexible organic free radical electrode |
-
2012
- 2012-02-27 CN CN2012100465902A patent/CN102593436A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008124167A1 (en) * | 2007-04-10 | 2008-10-16 | The Regents Of The University Of California | Charge storage devices containing carbon nanotube films as electrodes and charge collectors |
| CN101315974A (en) * | 2007-06-01 | 2008-12-03 | 清华大学 | Lithium ionic cell cathode and method for producing the same |
| CN101388447A (en) * | 2007-09-14 | 2009-03-18 | 清华大学 | Negative pole for lithium ionic cell and prepraring method thereof |
| CN101420021A (en) * | 2007-10-26 | 2009-04-29 | 清华大学 | Positive pole of lithium ion cell and preparation method thereof |
| CN101582302A (en) * | 2008-05-14 | 2009-11-18 | 清华大学 | Carbon nano tube/conductive polymer composite material |
| US20110256451A1 (en) * | 2009-12-21 | 2011-10-20 | Cui li-feng | Nanotube-based nanomaterial membrane |
| CN102270761A (en) * | 2010-06-03 | 2011-12-07 | 上海空间电源研究所 | Method for making integrated flexible organic free radical electrode |
Non-Patent Citations (3)
| Title |
|---|
| PO-CHIANG CHEN等: "Preparation and Characterization of Flexible Asymmetric Supercapacitors Based on Transition-Metal-Oxide Nanowire/Single-Walled Carbon Nanotube Hybrid Thin-Film Electrodes", 《ACS NANO》 * |
| XILAI JIA等: "High-performance flexible lithium-ion electrodes based on robust network architecture", 《ENERGY & ENVIRONMENTAL SCIENCE》 * |
| 崔同湘等: "碳纳米管纸的制备研究进展", 《材料导报》 * |
Cited By (64)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103682368A (en) * | 2012-09-20 | 2014-03-26 | 中国科学院金属研究所 | Rapidly charged flexible lithium ion battery and preparation method of electrodes of rapidly charged flexible lithium ion battery |
| CN102945947A (en) * | 2012-12-04 | 2013-02-27 | 中国科学院上海硅酸盐研究所 | Preparation method of flexible binding agent-free self-support combination electrode |
| CN103325998A (en) * | 2013-05-15 | 2013-09-25 | 同济大学 | Flexible nano SnO2/Si composite lithium ion battery negative-electrode material and preparation method thereof |
| CN103325998B (en) * | 2013-05-15 | 2016-01-20 | 同济大学 | Flexible nano SnO 2/ Si complex lithium ion battery cathode material and preparation method thereof |
| CN103280581A (en) * | 2013-05-20 | 2013-09-04 | 中国科学院过程工程研究所 | Negative material of lithium-ion battery and preparation method of negative material |
| CN103337632A (en) * | 2013-07-10 | 2013-10-02 | 肖辉 | Carbon nanopaper supported lithium iron phosphate lithium ion positive electrode and making method thereof |
| CN103337632B (en) * | 2013-07-10 | 2015-09-09 | 昆明纳太能源科技有限公司 | A kind of carbon nanometer paper load ferrous phosphate lithium ion positive pole and preparation method thereof |
| CN103413927B (en) * | 2013-08-12 | 2015-04-29 | 浙江大学 | Lithium titanate/iron sesquioxide composite lithium ion battery cathode material and preparation method thereof |
| CN103413927A (en) * | 2013-08-12 | 2013-11-27 | 浙江大学 | Lithium titanate/iron sesquioxide composite lithium ion battery cathode material and preparation method thereof |
| CN103682307A (en) * | 2013-11-27 | 2014-03-26 | 山东精工电子科技有限公司 | LiNi0.5Mn1.5O4/lithium titanate battery and preparation method thereof |
| CN103682307B (en) * | 2013-11-27 | 2017-01-04 | 山东精工电子科技有限公司 | Nickel ion doped/lithium titanate battery and preparation method thereof |
| CN103730630A (en) * | 2013-12-25 | 2014-04-16 | 北京大学深圳研究生院 | Combined electrode of battery and preparation method thereof |
| CN104752731B (en) * | 2013-12-25 | 2018-05-08 | 比亚迪股份有限公司 | A kind of flexible lithium ion battery collector, flexible lithium ion battery and preparation method thereof |
| CN104752731A (en) * | 2013-12-25 | 2015-07-01 | 比亚迪股份有限公司 | Flexible lithium ion battery current collector, flexible lithium ion battery and preparation method of flexible lithium ion battery |
| CN103779106A (en) * | 2013-12-31 | 2014-05-07 | 昆明纳太能源科技有限公司 | Nanometer carbon paper for super-capacitor and preparing method thereof |
| CN103904366A (en) * | 2014-03-09 | 2014-07-02 | 复旦大学 | Flexible linear lithium ion battery and preparation method thereof |
| CN103904366B (en) * | 2014-03-09 | 2016-08-17 | 宁国市龙晟柔性储能材料科技有限公司 | A kind of flexible wire lithium ion battery and preparation method thereof |
| CN104241601A (en) * | 2014-07-02 | 2014-12-24 | 宁波艾特米克锂电科技有限公司 | Preparation method of metal-current-collector-free lithium battery or super-capacitor electrode |
| CN104505498A (en) * | 2014-12-12 | 2015-04-08 | 天津大学 | Preparation method of ferric oxide/carbon nanotube lithium ion battery anode material |
| CN104795540B (en) * | 2015-03-17 | 2017-03-08 | 江苏乐能电池股份有限公司 | A kind of preparation method of high-energy-density flexible package winding battery |
| CN104795540A (en) * | 2015-03-17 | 2015-07-22 | 江苏乐能电池股份有限公司 | Making method of flexibly packaged coiled battery with high specific energy |
| CN105185965A (en) * | 2015-09-23 | 2015-12-23 | 清华大学 | Flexible carbon-sulfur composite cathode material for lithium-sulfur battery |
| CN105551824A (en) * | 2015-12-17 | 2016-05-04 | 上海奥威科技开发有限公司 | Self-support supercapacitor free of metallic current collector |
| US11383213B2 (en) | 2016-03-15 | 2022-07-12 | Honda Motor Co., Ltd. | System and method of producing a composite product |
| US11888152B2 (en) | 2016-03-15 | 2024-01-30 | Honda Motor Co., Ltd. | System and method of producing a composite product |
| US11171324B2 (en) | 2016-03-15 | 2021-11-09 | Honda Motor Co., Ltd. | System and method of producing a composite product |
| CN106374099A (en) * | 2016-11-02 | 2017-02-01 | 哈尔滨工业大学 | Flexible self-supporting lithium-rich manganese-based cathode for lithium ion battery and preparation method thereof |
| CN106374099B (en) * | 2016-11-02 | 2019-07-16 | 哈尔滨工业大学 | A kind of lithium ion battery flexible self-supporting lithium-rich manganese-based anode and preparation method thereof |
| CN108122686A (en) * | 2016-11-28 | 2018-06-05 | 中国科学院大连化学物理研究所 | The Li of fluoride cladding4Ti5O12/ carbon nanotubes composite negative pole material and its preparation and application |
| CN108122686B (en) * | 2016-11-28 | 2019-08-02 | 中国科学院大连化学物理研究所 | The Li of fluoride cladding4Ti5O12/ carbon nanotube composite negative pole material and its preparation and application |
| US11081684B2 (en) | 2017-05-24 | 2021-08-03 | Honda Motor Co., Ltd. | Production of carbon nanotube modified battery electrode powders via single step dispersion |
| US11735705B2 (en) | 2017-05-24 | 2023-08-22 | Honda Motor Co., Ltd. | Production of carbon nanotube modified battery electrode powders via single step dispersion |
| CN107394159A (en) * | 2017-07-24 | 2017-11-24 | 江苏大学 | A kind of composite fibre negative material and preparation method thereof |
| US11569490B2 (en) | 2017-07-31 | 2023-01-31 | Honda Motor Co., Ltd. | Continuous production of binder and collector-less self-standing electrodes for Li-ion batteries by using carbon nanotubes as an additive |
| US11374214B2 (en) | 2017-07-31 | 2022-06-28 | Honda Motor Co., Ltd. | Self standing electrodes and methods for making thereof |
| US10658651B2 (en) | 2017-07-31 | 2020-05-19 | Honda Motor Co., Ltd. | Self standing electrodes and methods for making thereof |
| CN109509866A (en) * | 2017-09-15 | 2019-03-22 | 本田技研工业株式会社 | By the method for cell connector attachment structure self-supporting electrode |
| US11489147B2 (en) | 2017-09-15 | 2022-11-01 | Honda Motor Co., Ltd. | Method for embedding a battery tab attachment in a self-standing electrode without current collector or binder |
| US11616221B2 (en) | 2017-09-15 | 2023-03-28 | Honda Motor Co., Ltd. | Method for battery tab attachment to a self-standing electrode |
| US11201318B2 (en) | 2017-09-15 | 2021-12-14 | Honda Motor Co., Ltd. | Method for battery tab attachment to a self-standing electrode |
| CN109509866B (en) * | 2017-09-15 | 2023-05-26 | 本田技研工业株式会社 | Self-supporting electrode and method for manufacturing the same |
| US11121358B2 (en) | 2017-09-15 | 2021-09-14 | Honda Motor Co., Ltd. | Method for embedding a battery tab attachment in a self-standing electrode without current collector or binder |
| CN109755497A (en) * | 2017-11-08 | 2019-05-14 | 株式会社Lg化学 | Electrode with three-dimensional structure and the electrochemical appliance comprising it |
| US11646426B2 (en) | 2017-11-08 | 2023-05-09 | Ulsan National Institute Of Science And Technology | Electrode having three dimensional structure and electrochemical device including the same |
| CN109755497B (en) * | 2017-11-08 | 2022-10-25 | 株式会社Lg新能源 | Electrode having three-dimensional structure and electrochemical device comprising the same |
| CN108807884A (en) * | 2018-05-31 | 2018-11-13 | 中国科学院过程工程研究所 | A kind of system and method for lithium ion battery negative material carbon coating modification |
| CN108842140B (en) * | 2018-05-31 | 2020-10-23 | 中国科学院过程工程研究所 | System and method for carbon coating modification of lithium ion battery anode material |
| CN108842140A (en) * | 2018-05-31 | 2018-11-20 | 中国科学院过程工程研究所 | A kind of system and method for anode material for lithium-ion batteries coated modified carbon |
| CN108807884B (en) * | 2018-05-31 | 2020-10-23 | 中国科学院过程工程研究所 | Device and method for carbon-coated modification of lithium ion battery negative electrode material |
| CN108987796A (en) * | 2018-09-10 | 2018-12-11 | 江西克莱威纳米碳材料有限公司 | A kind of flexible lithium ion battery and preparation method thereof |
| CN109273755A (en) * | 2018-09-25 | 2019-01-25 | 福建省致格新能源电池科技有限公司 | A kind of flexibility secondary cell and its component |
| CN109742327A (en) * | 2018-12-29 | 2019-05-10 | 西安鸿钧睿泽新材料科技有限公司 | Preparation method of self-supporting flexible lithium ion battery carbon cloth loaded LiFePO4 positive electrode material |
| US11535517B2 (en) | 2019-01-24 | 2022-12-27 | Honda Motor Co., Ltd. | Method of making self-standing electrodes supported by carbon nanostructured filaments |
| CN111477871A (en) * | 2019-01-24 | 2020-07-31 | 本田技研工业株式会社 | Method of making free-standing electrodes supported by carbon nanostructured filaments |
| US11352258B2 (en) | 2019-03-04 | 2022-06-07 | Honda Motor Co., Ltd. | Multifunctional conductive wire and method of making |
| US11325833B2 (en) | 2019-03-04 | 2022-05-10 | Honda Motor Co., Ltd. | Composite yarn and method of making a carbon nanotube composite yarn |
| US11834335B2 (en) | 2019-03-04 | 2023-12-05 | Honda Motor Co., Ltd. | Article having multifunctional conductive wire |
| US11539042B2 (en) | 2019-07-19 | 2022-12-27 | Honda Motor Co., Ltd. | Flexible packaging with embedded electrode and method of making |
| CN111525114A (en) * | 2020-05-09 | 2020-08-11 | 四川聚创石墨烯科技有限公司 | Method for continuously preparing current collector-free silicon-carbon negative electrode paper |
| CN112176771A (en) * | 2020-09-25 | 2021-01-05 | 柔电（武汉）科技有限公司 | Preparation method of lithium-philic carbon nanotube paper and preparation method of composite metal lithium cathode |
| CN112467104A (en) * | 2020-11-23 | 2021-03-09 | 复旦大学 | Preparation method of lithium cobaltate thick electrode |
| CN113793931A (en) * | 2021-11-18 | 2021-12-14 | 河南电池研究院有限公司 | Iron oxide negative electrode material for lithium ion battery and preparation method thereof |
| CN115403033A (en) * | 2022-10-09 | 2022-11-29 | 清华大学 | Conductive agent for lithium ion battery, negative electrode and preparation method thereof, and lithium ion battery |
| CN115403033B (en) * | 2022-10-09 | 2024-01-30 | 清华大学 | Conductive agent for lithium ion battery, negative electrode and preparation method thereof, and lithium ion battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102593436A (en) | Self-supporting flexible carbon nano-tube paper composite electrode material for lithium ion battery | |
| Zhang et al. | Tin quantum dots embedded in nitrogen-doped carbon nanofibers as excellent anode for lithium-ion batteries | |
| JP6445585B2 (en) | Porous carbon nanotube microspheres and production method and use thereof, metallic lithium-skeleton carbon composite material and production method thereof, negative electrode, and battery | |
| Xia et al. | Ultrafine LiMn2O4/carbon nanotube nanocomposite with excellent rate capability and cycling stability for lithium-ion batteries | |
| Xiao et al. | A facile PVP-assisted hydrothermal fabrication of Fe2O3/Graphene composite as high performance anode material for lithium ion batteries | |
| CN103500820B (en) | A kind of sulphur for lithium-sulfur cell/porous carbon enveloped carbon nanometer tube composite positive pole and preparation method thereof | |
| Li et al. | Electrospun porous vanadium pentoxide nanotubes as a high-performance cathode material for lithium-ion batteries | |
| CN108172770B (en) | Carbon-coated NiP with monodisperse structural featuresxNano composite electrode material and preparation method thereof | |
| Sun et al. | Fe2O3/CNTs composites as anode materials for lithium-ion batteries | |
| Tan et al. | Mesoporous LiFePO4 microspheres embedded homogeneously with 3D CNT conductive networks for enhanced electrochemical performance | |
| CN102082264B (en) | Method for preparing presoma of active electrode material of nano-lithium ion battery and application thereof | |
| Zhang et al. | Fabricating high performance lithium-ion batteries using bionanotechnology | |
| CN105390687A (en) | High-performance three-dimensional carbon nanotube composite negative electrode material, preparation method therefor and application thereof | |
| Adepoju et al. | High C-rate performance of LiFePO4/carbon nanofibers composite cathode for Li-ion batteries | |
| Wang et al. | Facile construction of high-performance amorphous FePO4/carbon nanomaterials as cathodes of lithium-ion batteries | |
| Jin et al. | Pomegranate-like Li3VO4/3D graphene networks nanocomposite as lithium ion battery anode with long cycle life and high-rate capability | |
| CN103779564A (en) | High-performance sodium vanadyl phosphate symmetrical sodium-ion battery material and preparation method and application thereof | |
| CN103560231A (en) | Lithium ion battery anode composite material and its preparation method | |
| CN105702958B (en) | Preparation method and application of tin dioxide quantum dot solution and composite material thereof | |
| CN102306774B (en) | Lithium iron phosphate nano array serving as cathode material of lithium ion battery and preparation method of lithium iron phosphate nano array | |
| Luo et al. | Carbon nanotube-modified LiFePO4 for high rate lithium ion batteries | |
| CN107331839A (en) | A kind of preparation method of carbon nanotube loaded nano titanium oxide | |
| CN102760880A (en) | High power iron phosphate ion battery material and preparation method thereof | |
| Hou et al. | Facile spray-drying/pyrolysis synthesis of intertwined SiO@ CNFs&G composites as superior anode materials for Li-ion batteries | |
| Chen et al. | Biomass-mediated synthesis of carbon-supported ZnMn2O4 nanoparticles as high-performance anode materials for lithium-ion batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120718 |