CN102655229B - Pore-forming method for diaphragms of lithium ion batteries - Google Patents
Pore-forming method for diaphragms of lithium ion batteries Download PDFInfo
- Publication number
- CN102655229B CN102655229B CN201210078193.3A CN201210078193A CN102655229B CN 102655229 B CN102655229 B CN 102655229B CN 201210078193 A CN201210078193 A CN 201210078193A CN 102655229 B CN102655229 B CN 102655229B
- Authority
- CN
- China
- Prior art keywords
- diaphragm
- pore
- creating material
- pore creating
- material solution
- 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.)
- Active
Links
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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a pore-forming method for diaphragms of lithium ion batteries. The method comprises the following steps: fully dissolving a pore-forming agent into a solvent so as to prepare a pore-forming agent solution; uniformly coating the pore-forming agent solution on the surface of a to-be-cold-pressed diaphragm, and carrying out baking on the diaphragm at a temperature lower than the sublimation or decomposition temperature of the pore-forming agent, so that a solvent of the pore-forming agent solution is volatilized, and the pore-forming agent is recrystallized in the diaphragm; and carrying out cold pressing on the diaphragm, and then carrying out baking on the diaphragm at a temperature higher than the sublimation or decomposition temperature of the pore-forming agent, so that the pore-forming agent recrystallized in the diaphragm is sublimated or decomposed, thereby obtaining a porous diaphragm. According to the invention, through regulating the viscosity of the pore-forming agent solution, a diaphragm with adjustably-distributed pores can be obtained, and the regulating method is simple and flexible, and wide in applicable range; and particularly, according to the invention, an efficient gradient pore distribution structure that more pores are distributed on the surface layer of the diaphragm and less pores are distributed on the inner layer of the diaphragm can be realized just through selecting an appropriate viscosity of the pore-forming agent solution..
Description
Technical field
The invention belongs to technical field of lithium ion, particularly a kind of pore forming method of lithium ion battery diaphragm.
Background technology
Since the extensive commercialization of lithium ion battery, rely on the advantage of its high-energy-density, high power density, be widely used in as laptop computer, video camera, mobile communication at portable electronics.But along with the continuous renewal of consumer electronics product design and constantly broadening of application demand scope, its requirement to battery performance (as charge-discharge performance fast, good cryogenic property) also improves constantly.
Known to people in the industry, the fast conducting of two passages of battery system is depended in the raising of battery performance: ion channel and electron channel.For the fast conducting of ion channel, key is the vesicular structure in electrode diaphragm.Vesicular structure is good, and electrolyte just can infiltrate each particle in diaphragm fully rapidly; In charge and discharge process, lithium ion just can infiltrate network fast conducting between positive and negative electrode by this electrolyte, shows good electrical property.
For the regulation and control of the vesicular structure of electrode diaphragm, it is mainly to realize by controlling compacted density size that industry is produced.But this method can only realize the entirety of diaphragm mesopore density to be become large or diminishes, and reduction compacted density can cause battery core energy density to reduce.Diaphragm is colded pressing and also can be caused that top layer pore size distribution is few, bottom pore size distribution is many, and this is a vesicular structure that is unfavorable for electrolyte and ion fast conducting, because the flow maximum that the diffusion of top layer electrolyte and ion spread, laminar flow amount is less more inward.So wishing to obtain general is the fewer structures of many, the more past bottom pore size distributions of top layer pore size distribution, and such hole structure can ensure the fast conducting of fully infiltrating fast of electrolyte and ion; And to construct the space taking minimum in such hole, can provide maximum spaces to improve battery core energy density to active material.
Based on patent and literature survey, some other can regulate method of the hole structure of electrode diaphragm to mainly contain to add in slurry these two kinds of pore creating material port-creating method and diaphragm punch methods.The former can affect to formula of size selection and pulping process because pore creating material will be added to this highstrung metastable system of slurry; And if manufacture hole, top layer is many, few this efficient vesicular structure in nexine hole, the method need to be prepared the slurry of different pore creating material concentration and carry out multi-layer coated could realization, and this is a very complicated process of operation.Diaphragm punch method is mainly in diaphragm, to produce specific hole structure by the method for machinery/physics, in the method implementation process, will cause machinery/physical damage to the active material in diaphragm, causes the reduction of battery core energy density; And in the method short time, be difficult to realize on a large scale, produce in batches efficiently, in addition, diaphragm punch method also needs to use expensive precision instrument and equipment.
In view of this, necessaryly provide a kind of and can produce that pore size distribution in diaphragm is adjustable, operation implements pore forming method simple, to the friendly lithium ion battery diaphragm that can mass production without destroying, in the short time of diaphragm active material.
Summary of the invention
The object of the invention is to: for the deficiencies in the prior art, and provide a kind of and can produce that pore size distribution in diaphragm is adjustable, operation implements pore forming method simple, to the friendly lithium ion battery diaphragm that can mass production without destroying, in the short time of diaphragm active material.
In order to achieve the above object, the present invention adopts following technical scheme:
A pore forming method for lithium ion battery diaphragm, comprises the following steps:
Step 1, chooses required pore creating material and corresponding solvent, according to the requirement of pore creating material solution concentration and viscosity is fully dissolved in pore creating material in pore creating material solution solvent by required proportioning, is uniformly dispersed, and prepares pore creating material solution;
Step 2, the pore creating material solution that step 1 is obtained is coated in membrane surface to be colded pressing equably, pore creating material solution is penetrated into diaphragm inside by existing hole in diaphragm, at lower than pore creating material distillation or the temperature of decomposing, diaphragm is toasted, make the volatilization of pore creating material solution solvent, pore creating material is at the inner recrystallization of diaphragm and occupy certain aperture position;
Step 3, colds pressing to diaphragm, then at the temperature higher than pore creating material distillation or decomposition, toasts, and makes pore creating material distillation or decomposition at the inner recrystallization of diaphragm, thereby in diaphragm, leaves hole, obtains porous membrane.
Improve as the one of lithium ion battery diaphragm pore forming method of the present invention, described pore creating material is benzoic acid, oxalic acid and at least one in ball how.These materials have ambient stable, but the feature that heating easily distils or decomposes.
One as lithium ion battery diaphragm pore forming method of the present invention is improved, and described solvent is at least one in nitrogen methyl pyrrolidone (NMP), acetone, ethanol or water.These solvents can fully dissolve pore creating material.
One as lithium ion battery diaphragm pore forming method of the present invention is improved, and the viscosity of described solvent is 1mPas ~ 1000mPas.The osmotic resistance of high viscosity pore creating material solution in diaphragm is large, is mainly distributed in diaphragm top layer; Low viscous pore creating material solution, the osmotic resistance in diaphragm is little, is all penetrated into very soon diaphragm bottom; The pore creating material solution of proper viscosity, the osmotic resistance in diaphragm is suitable, can uniformly penetrating in whole diaphragm.
Improve as the one of lithium ion battery diaphragm pore forming method of the present invention, the viscosity of described solvent is 300mPas ~ 1000mPas, and to prepare diaphragm, to be hole, top layer many, the distribution that nexine hole is few.
One as lithium ion battery diaphragm pore forming method of the present invention is improved, and the concentration of described pore creating material solution is 0.1mol/L ~ 10mol/L.The design of pore creating material solution concentration need to be considered the requirement of pore creating material solution viscosity and pore-creating volume simultaneously, is ensureing, under the prerequisite of pore size distribution gradient in diaphragm thickness direction, to reach the requirement to pore-creating volume.
One as lithium ion battery diaphragm pore forming method of the present invention is improved, and described pore creating material solution is coated on diaphragm by the mode of spraying, brushing, dip-coating or extrusion coated.
Improve as the one of lithium ion battery diaphragm pore forming method of the present invention, the temperature of toasting described in step 3 is less than or equal to 180 DEG C, to avoid that the bonding agent in diaphragm is caused to burn-in effects.
Improve as the one of lithium ion battery diaphragm pore forming method of the present invention, baking is vacuum bakeout described in step 3, and vacuum degree is higher than-80KPa, to avoid as far as possible the oxidation of bonding agent in the oxidation of diaphragm collector and diaphragm.
Improve as the one of lithium ion battery diaphragm pore forming method of the present invention, described in diaphragm to be colded pressing be anodal diaphragm and/or cathode membrane.
Compared with prior art, the present invention at least tool have the following advantages:
The first, in the present invention, realize adding after diaphragm prepares of pore creating material by being coated with pore creating material solution, do not relate to the pulping process to pore creating material sensitivity, formula of size do not had restricted;
The second, the present invention, by regulating the viscosity of pore creating material solution, can obtain the adjustable diaphragm of pore size distribution, and control method simple and flexible is applied widely; Especially, for realizing the hole structure of the gradient distribution that hole, diaphragm top layer is many, nexine hole is few, the present invention is without the slurry of the different pore creating material concentration of preparation, also multi-layer coated without carrying out, only need by selecting suitable pore creating material solution viscosity (by selecting different pore creating material solution solvent and selecting different pore creating material solution concentrations to realize) to realize easily.
The 3rd, compare normal battery core production process, the present invention realizes simply, only need between diaphragm painting process and diaphragm cold pressing process, increase the process (and pore creating material distillation/decomposition completes in can merging to the diaphragm vacuum process of colding pressing normally together) that is coated with together pore creating material solution and baking volatilization pore creating material solution solvent.So the present invention there is no impact to current battery production process efficiency, can realize at short notice mass production.
The 4th, the inventive method can not destroyed the active material in pole piece, can not impact the capacity of battery; And this pore-creating is with low cost, without buying expensive accurate punch device.
Embodiment
The pore forming method of describing lithium ion battery diaphragm of the present invention below in conjunction with specific embodiment in detail, still, embodiments of the invention are not limited to this.
embodiment 1
Get 0.1mol benzoic acid powder and be fully dissolved in 1L nitrogen methyl pyrrolidone (NMP) solvent, prepare the pore creating material solution of 0.1mol/L, pore creating material solution viscosity is 1mPas.Get graphite cathode diaphragm coated, before colding pressing, adopt spraying process to be coated with last layer pore creating material solution at its surface uniform.Because pore creating material solution viscosity is very low, diaphragm is very little to the osmotic resistance of pore creating material solution, and most of pore creating material solution will be penetrated into diaphragm bottom.Carry out 85 DEG C of bakings 10 minutes to being coated with the diaphragm of pore creating material solution, NMP is fully volatilized, benzoic acid solute crystallization occupy certain position at diaphragm bottom hole place again simultaneously.Then, to implanted Benzoic Acid Crystal diaphragm cold pressing; Then to the diaphragm of having colded pressing at 110 DEG C of vacuum bakeout 6h (vacuum degree-99Kpa); In bake process, Benzoic Acid Crystal distillation becomes gas and spins off from diaphragm, thereby in diaphragm, leaves a series of hole.Because the pore creating material solution major part of spraying has been penetrated into diaphragm bottom, so what make in this embodiment is that bottom hole is many, Kong Shao hole, top layer structure.
embodiment 2
Get 1mol oxalic acid powder and be fully dissolved in 1L pure water solvent, prepare the pore creating material solution of 1mol/L, pore creating material solution viscosity is 100mPas.Get lithium cobaltate cathode diaphragm coated, before colding pressing, adopt spread coating to be coated with last layer pore creating material solution at its surface uniform.Because pore creating material solution viscosity is moderate, only there is suitable resistance to the infiltration of pore creating material solution in diaphragm, and uniformly penetrating is arrived diaphragm inside by pore creating material solution.Carry out 100 DEG C of bakings 15 minutes to being coated with the diaphragm of pore creating material solution, aqueous solvent is fully volatilized, oxalic acid solute crystallization occupy certain position at diaphragm bottom hole place again simultaneously.Then, to implanted oxalic acid crystal diaphragm cold pressing; Then to the diaphragm of having colded pressing at 110 DEG C of vacuum bakeout 6h (vacuum degree-99Kpa); In bake process, the distillation of oxalic acid crystal becomes gas and spins off from diaphragm, thereby in diaphragm, leaves a series of hole.Because the pore creating material solution uniformly penetrating of brushing has arrived diaphragm inside, so what make in this embodiment is equally distributed hole structure in diaphragm thickness direction.
embodiment 3
How ball powder is fully dissolved in 1L alcohol solvent to get 10mol, prepares the pore creating material solution of 10mol/L, and pore creating material solution viscosity is 900mPas.Get iron phosphate lithium positive pole diaphragm coated, before colding pressing, adopt extrusion coated method to be coated with last layer pore creating material solution at its surface uniform.Because pore creating material solution viscosity is high, diaphragm is very large to the osmotic resistance of pore creating material solution, only has a small amount of pore creating material solution can be penetrated into diaphragm bottom.Carry out 45 DEG C of bakings 10 minutes to being coated with the diaphragm of pore creating material solution, ethanol is fully volatilized, simultaneously how ball solute crystallization occupy certain position at diaphragm bottom hole place again.Then, to implanted ball crystal how diaphragm cold pressing; Then to the diaphragm of having colded pressing at 110 DEG C of vacuum bakeout 6h (vacuum degree-99Kpa); In bake process, how the distillation of ball crystal becomes gas spins off from diaphragm, thereby in diaphragm, leaves a series of hole.Because the pore creating material solution of extrusion coated only has small part to be penetrated into diaphragm bottom, so what make in this embodiment is that hole, top layer is many, the hole structure that bottom hole is few.
embodiment 4
Get 10mol benzoic acid powder and be fully dissolved in 1L nitrogen methyl pyrrolidone (NMP) solvent, prepare the pore creating material solution of 10mol/L, pore creating material solution viscosity is 1000mPas.Get lithium titanate anode diaphragm coated, before colding pressing, adopt dip coating to be coated with last layer pore creating material solution at its surface uniform.Because pore creating material solution viscosity is very high, diaphragm is very large to the osmotic resistance of pore creating material solution, only has fraction pore creating material solution will be penetrated into diaphragm bottom.Carry out 85 DEG C of bakings 10 minutes to being coated with the diaphragm of pore creating material solution, NMP is fully volatilized, benzoic acid solute crystallization occupy certain position at diaphragm bottom hole place again simultaneously.Then, to implanted Benzoic Acid Crystal diaphragm cold pressing; Then to the diaphragm of having colded pressing at 110 DEG C of vacuum bakeout 6h (vacuum degree-99Kpa); In bake process, Benzoic Acid Crystal distillation becomes gas and spins off from diaphragm, thereby in diaphragm, leaves a series of hole.Because the pore creating material solution of spraying only has fraction to be penetrated into diaphragm bottom, so what make in this embodiment is that bottom hole is few, Kong Duo hole, top layer structure.
embodiment 5
How ball powder is fully dissolved in 1L acetone solvent to get 5mol, prepares the pore creating material solution of 5mol/L, and pore creating material solution viscosity is 500mPas.Get silicon alloy cathode membrane coated, before colding pressing, adopt spread coating to be coated with last layer pore creating material solution at its surface uniform.Because pore creating material solution viscosity is higher, diaphragm is larger to the osmotic resistance of pore creating material solution, only has fraction pore creating material solution will be penetrated into diaphragm bottom.Carry out 85 DEG C of bakings 10 minutes to being coated with the diaphragm of pore creating material solution, acetone is fully volatilized, simultaneously how ball solute crystallization occupy certain position at diaphragm bottom hole place again.Then, to implanted ball crystal how diaphragm cold pressing; Then to the diaphragm of having colded pressing at 110 DEG C of vacuum bakeout 6h (vacuum degree-85Kpa); In bake process, how the distillation of ball crystal becomes gas spins off from diaphragm, thereby in diaphragm, leaves a series of hole.Because the pore creating material solution of spraying only has fraction to be penetrated into diaphragm bottom, so what make in this embodiment is that bottom hole is few, Kong Duo hole, top layer structure.
In sum, the present invention adopts the solution that is coated with pore creating material on the membrane surface before colding pressing, and colds pressing, afterwards this diaphragm after colding pressing by heat treatment again after the complete recrystallization of pore creating material, make pore creating material distillation or decompose, thereby in diaphragm, producing pore-creating effect; By the viscosity of pore creating material solution is controlled, can regulate easily the osmotic resistance of pore-creating diaphragm to pore creating material solution, thereby regulate the implantation amount of pore creating material at diaphragm different depth place, finally obtain the hole structure along diaphragm thickness direction different distributions trend.
The present invention, by regulating the viscosity of pore creating material solution, can obtain the adjustable diaphragm of pore size distribution, and control method simple and flexible is applied widely; Especially, for realizing the hole structure of the gradient distribution that hole, diaphragm top layer is many, nexine hole is few, the present invention is without the slurry of the different pore creating material concentration of preparation, also multi-layer coated without carrying out, only need by selecting suitable pore creating material solution viscosity (by selecting different pore creating material solution solvent and selecting different pore creating material solution concentrations to realize) to realize easily.The hole structure that the gradient that hole, diaphragm top layer is many, nexine hole is few distributes can ensure the fast conducting of fully infiltrating fast of electrolyte and ion; And to construct the space taking minimum in such hole, can provide maximum spaces to improve battery core energy density to active material.
In addition, compare normal battery core production process, the present invention realizes simply, only need between diaphragm painting process and diaphragm cold pressing process, increase the process (and pore creating material distillation/decomposition completes in can merging to the diaphragm vacuum process of colding pressing normally together) that is coated with together pore creating material solution and baking volatilization pore creating material solution solvent.So the present invention there is no impact to current battery production process efficiency, can realize at short notice mass production.
It should be noted that, the announcement of book and elaboration according to the above description, those skilled in the art in the invention can also change and revise above-mentioned execution mode.Therefore, the present invention is not limited to embodiment disclosed and described above, also should be in the protection range of claim of the present invention to equivalent modifications more of the present invention and change.In addition,, although used some specific terms in this specification, these terms just for convenience of description, do not form any restriction to the present invention.
Claims (6)
1. a pore forming method for lithium ion battery diaphragm, is characterized in that, comprises the following steps:
Step 1, is fully dissolved in pore creating material in solvent, prepares pore creating material solution;
Step 2, the pore creating material solution that step 1 is obtained is coated in membrane surface to be colded pressing equably, pore creating material solution is penetrated into diaphragm inside by existing hole in diaphragm, at lower than pore creating material distillation or the temperature of decomposing, diaphragm is toasted, make the volatilization of pore creating material solution solvent, pore creating material is at the inner recrystallization of diaphragm and occupy certain position at diaphragm bottom hole place;
Step 3, colds pressing to the diaphragm of having implanted pore creating material, then at the temperature higher than pore creating material distillation or decomposition, toasts, and makes pore creating material distillation or decomposition at the inner recrystallization of diaphragm, thereby in diaphragm, leaves hole, obtains porous membrane;
Described pore creating material is benzoic acid, oxalic acid and at least one in ball how;
Described solvent is at least one in nitrogen methyl pyrrolidone (NMP), acetone, ethanol or water;
The viscosity of described pore creating material solution is 1mPas ~ 1000mPas;
The concentration of described pore creating material solution is 0.1mol/L ~ 10mol/L.
2. lithium ion battery diaphragm pore forming method according to claim 1, is characterized in that: the viscosity of described pore creating material solution is 300mPas ~ 1000mPas.
3. lithium ion battery diaphragm pore forming method according to claim 1, is characterized in that: described pore creating material solution is coated on diaphragm by the mode of spraying, brushing, dip-coating or extrusion coated.
4. lithium ion battery diaphragm pore forming method according to claim 1, is characterized in that: the temperature of toasting described in step 3 is less than or equal to 180 DEG C.
5. lithium ion battery diaphragm pore forming method according to claim 1, is characterized in that: described in step 3, baking is for vacuum bakeout, and vacuum degree is higher than-80KPa.
6. lithium ion battery diaphragm pore forming method according to claim 1, is characterized in that: described in diaphragm to be colded pressing be anodal diaphragm and/or cathode membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210078193.3A CN102655229B (en) | 2012-03-19 | 2012-03-19 | Pore-forming method for diaphragms of lithium ion batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210078193.3A CN102655229B (en) | 2012-03-19 | 2012-03-19 | Pore-forming method for diaphragms of lithium ion batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102655229A CN102655229A (en) | 2012-09-05 |
| CN102655229B true CN102655229B (en) | 2014-11-05 |
Family
ID=46730814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210078193.3A Active CN102655229B (en) | 2012-03-19 | 2012-03-19 | Pore-forming method for diaphragms of lithium ion batteries |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102655229B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104157827A (en) * | 2013-05-14 | 2014-11-19 | 深圳华粤宝电池有限公司 | Lithium ion battery negative film and preparation method thereof |
| CN109167020B (en) * | 2018-09-11 | 2021-03-30 | 天津市捷威动力工业有限公司 | Porous lithium ion pole piece with high energy density, preparation method thereof and lithium ion battery |
| CN110729494A (en) * | 2019-10-30 | 2020-01-24 | 无锡威孚高科技集团股份有限公司 | Catalyst slurry for proton exchange membrane fuel cell and preparation method thereof |
| CN111244395A (en) * | 2020-01-22 | 2020-06-05 | 苏州易来科得科技有限公司 | Lithium ion pole piece, preparation method thereof and lithium ion battery |
| CN111900306A (en) * | 2020-07-13 | 2020-11-06 | 江苏可兰素环保科技有限公司 | High-energy-density lithium battery diaphragm and preparation method thereof |
| CN111900338A (en) * | 2020-09-15 | 2020-11-06 | 天津市捷威动力工业有限公司 | Preparation method of high-power thick electrode |
| CN113972373B (en) * | 2021-10-08 | 2023-05-26 | 浙江超恒动力科技有限公司 | Preparation method of lithium iron phosphate pole piece and lithium ion battery |
| CN114464816B (en) | 2022-04-12 | 2022-07-12 | 瑞浦兰钧能源股份有限公司 | Current collector with pore-forming functional coating, pole piece and lithium ion battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102197520A (en) * | 2008-10-27 | 2011-09-21 | 花王株式会社 | Process for producing positive electrode active material particles for battery |
| CN102324493A (en) * | 2011-08-26 | 2012-01-18 | 东莞新能源科技有限公司 | Thick electrode with good electrochemical performance and its preparation method |
-
2012
- 2012-03-19 CN CN201210078193.3A patent/CN102655229B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102197520A (en) * | 2008-10-27 | 2011-09-21 | 花王株式会社 | Process for producing positive electrode active material particles for battery |
| CN102324493A (en) * | 2011-08-26 | 2012-01-18 | 东莞新能源科技有限公司 | Thick electrode with good electrochemical performance and its preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102655229A (en) | 2012-09-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102655229B (en) | Pore-forming method for diaphragms of lithium ion batteries | |
| Xia et al. | Oxygen-deficient Ta2O5 nanoporous films as self-supported electrodes for lithium microbatteries | |
| Ren et al. | Core− shell Li3V2 (PO4) 3@ C composites as cathode materials for lithium-ion batteries | |
| CN105720236B (en) | A kind of sodium-ion battery cathode nickel foam self-supporting sheet Ni3P/C composite materials and preparation method thereof | |
| CN105140560B (en) | Stable lithium ion solid conductor of a kind of pair of lithium metal and preparation method thereof and a kind of all solid lithium secondary battery | |
| CN102280639B (en) | Transition metal element-doping and transition metal oxide-coating lithium iron phosphate composite anode material and preparation method | |
| CN103825000B (en) | Based on mesoporous carbon-loaded sulphur/selenium flexible electrode and preparation method thereof and the application of three-dimensional grapheme self supporting structure | |
| CN106876705A (en) | A kind of preparation method of fabricated in situ carbon/CNT coated lithium iron phosphate composite | |
| CN104934599B (en) | A kind of core shell structure lithium ion battery negative material manganese pyrophosphate and preparation method thereof | |
| CN108123134A (en) | A kind of porous fluorinated carbon material of Heteroatom doping and preparation method thereof | |
| CN110233285A (en) | A method of improving solid state battery interface stability using polymer dielectric | |
| CN102244234A (en) | Method for carbon-wrapped niobium-doped nanometer lithium titanate material | |
| CN104393304A (en) | Lithium-selenium battery positive electrode material, preparation method thereof and lithium-selenium battery | |
| CN108666613A (en) | A kind of solid electrolyte structure, secondary cell and preparation method | |
| CN103682275B (en) | Lithium ion battery composite cathode material vanadyl phosphate lithium-phosphoric acid vanadium lithium preparation method | |
| CN108963235A (en) | Graphene enhances carbon coating titanium phosphate manganese sodium micron ball electrode material and its preparation method and application | |
| CN108821256A (en) | A kind of nanometer fibrous anode material for lithium-ion batteries LiVPO4The preparation method of F | |
| CN103872289B (en) | A kind of ball-shaped lithium-ion battery anode material LiVPO4The preparation method of F | |
| CN107799321A (en) | The preparation method and lithium-ion capacitor of the nano oxidized lithium porous carbon composite of nano transition metal and lithium-ion capacitor | |
| CN112701268A (en) | Flexible integrated carbon-coated tungsten oxide/carbon nanotube film composite electrode and preparation method thereof | |
| CN110048094A (en) | A kind of self-supporting laminated film and preparation method thereof for liquid phase Zinc ion battery | |
| CN102299334A (en) | Carbon coated LiFePO4 porous anode and preparation method thereof | |
| Zhuang et al. | Metal–Organic Framework-Derived ZnO, N Dually Doped Nanocages as an Efficient Host for Stable Li Metal Anodes | |
| CN106549159A (en) | A kind of lithium-sulfur cell porous carbon materials and its preparation and application | |
| CN108417801A (en) | A kind of graphene In-situ reaction lithium iron phosphate positive material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |