CN104852004A - Secondary battery composite membrane, preparation method thereof and secondary battery - Google Patents
Secondary battery composite membrane, preparation method thereof and secondary battery Download PDFInfo
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- CN104852004A CN104852004A CN201410650151.1A CN201410650151A CN104852004A CN 104852004 A CN104852004 A CN 104852004A CN 201410650151 A CN201410650151 A CN 201410650151A CN 104852004 A CN104852004 A CN 104852004A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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- 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 provides a secondary battery composite membrane, a preparation method thereof and a secondary battery. The secondary battery composite membrane comprises an electric-insulated substrate layer and a conducting layer which is bonded to the surface of the electric-insulated substrate layer, and the conducting layer comprises conducting material, and the thickness of the conducting layer is 5 to 50 microns. The preparation method of the secondary battery composite membrane comprises the steps as follows: preparing dispersion liquid or slurry with conducting material, forming the conducting layer on the surface of the electric-insulated substrate layer by using the dispersion liquid or slurry with conducting material, drying and shaping the composite membrane, pressing the dried and shaped composite membrane. The membrane of the secondary battery uses the secondary battery composite membrane of the invention. The secondary battery composite membrane of the invention can be used for effectively preventing electrode material from falling off from a current collector so that the current collector can be used for charging and discharging continuously. The preparation method of the invention is high in production efficiency and can be applied in industrial production. The cycle life of the secondary battery is long.
Description
Technical field
The invention belongs to secondary battery technology, be specifically related to a kind of secondary cell composite diaphragm and preparation method thereof and a kind of secondary cell.
Background technology
Lithium rechargeable battery has the advantages such as open circuit voltage is high, specific capacity is high, memory-less effect, it is used widely in digital electronic goods field is as products such as mobile phone, digital camera and notebook computers, and is also applied to gradually among the big-and-middle-sized equipment such as electric automobile, intelligent grid.Along with the continuous expansion of lithium rechargeable battery range of application, its problem such as security performance and cycle life comes into one's own further.
Lithium rechargeable battery is primarily of part compositions such as positive pole, negative pole, electrolyte, barrier film, shells.Wherein, barrier film and electrode material are one of key components determining performance of lithium ion battery.In the actual application of battery, for performance of lithium ion battery, except fail safe and charge-discharge velocity, cycle life is also a very important reference index.
For electrode material, the research and development of a new generation's lithium ion battery are conceived to by using the electrode material of height ratio capacity to improve battery energy density, but, in the lithium-ion battery system using Novel high-specific capacity flexible electrode material (as silicon, metal oxide negative material and lithium-rich anode material), because electrode material change in volume in removal lithium embedded process is larger, electrode material is easily caused to come off inefficacy from current collector, and then causing battery capacity to fail rapidly, cycle life reduces greatly.At present for the main modified method of this kind of material be carry out adulterating around material itself, compound or nanometer etc.; although so can material property be improved; but usually greatly can increase the preparation cost of material or reduce material tap density, being difficult to be applied to large-scale industrial production.
For diaphragm material, its Main Function be as both positive and negative polarity between physical insulation barrier prevent internal short-circuit of battery, simultaneously for the diffusion of electrolyte intermediate ion provides path.The diaphragm material being applicable to lithium ion battery needs to possess following condition: good ionic conductivity and higher transference number of ions, to chemical stability and the electrochemical stability of electrolyte, good mechanical stretch performance and mechanical strength, to the abundant wetting capacity etc. of electrolyte.
According to the form that coexists of barrier film and electrolyte, barrier film used for lithium ion battery can be divided three classes: liquid-porous barrier film, semi liquid state barrier film and all solid state barrier film.Current commercial lithium-ion batteries barrier film great majority used are liquid-porous films, and electrolyte is present in barrier film hole in liquid form, has higher mechanical property and chemical stability.Linguistic term means for liquid-porous barrier film mainly contain: improve barrier film guarantor's liquid rate by improving barrier film porosity and then reduce battery internal resistance, improve battery security by regulation and control diaphragm closed pore temperature, improve barrier film ionic conductivity etc. by Material cladding; Main purpose concentrates on and improves battery security and charge-discharge velocity two aspect.
In order to improve the mechanical property of barrier film and lithium ion conduction performance and pick up, existing correlative study at present also obtains certain achievement, as disclosed a kind of organic-inorganic composite diaphragm at present, this composite diaphragm is made up of inorganic particle and high molecular polymer, inorganic particulate is evenly distributed in high molecular polymer, and gained composite diaphragm has good mechanical property and lithium ion conduction performance.Disclose the lithium ion battery separator of another kind of cellulose fiber base material at present, this barrier film by resistant to elevated temperatures cellulose as base material, then coating inorganic coating form, there is the resistance to elevated temperatures of good pick up and liquid-keeping property and excellence.
Because coming off of electrode material is the one of the main reasons causing existing secondary cell system cyclical stability to reduce, and the composite diaphragm of prior art report all uses insulating material as composite material, although the performances such as the intensity of barrier film self, pick up can be improved, but cannot play and tackle the electrode material that comes off and make it continue to realize the effect of discharge and recharge, therefore it cannot improve cycle performance of battery.
Summary of the invention
The object of the invention is to the above-mentioned deficiency overcoming prior art, a kind of secondary cell composite diaphragm and preparation method thereof is provided, be intended to solve existing secondary battery membrane can not tackle the electrode material that comes off and make it continue to realize discharge and recharge, the technical problem of cycle performance of battery cannot be improved.
Another object of the present invention is to provide a kind of secondary cell with good circulation performance.
In order to realize foregoing invention object, the technical scheme of the embodiment of the present invention is as follows:
A kind of secondary cell composite diaphragm, it conductive layer comprising electric insulation hypothallus and be combined in described electric insulation substrate layer surface, described conductive layer includes electric conducting material, and the thickness of described conductive layer is 5-50 μm.
And a kind of preparation method of secondary cell composite diaphragm, comprises the steps:
Be mixed with electric conducting material dispersion liquid by electric conducting material and surfactant-dispersed to liquid solvent, or electric conducting material and binding agent are added in solvent prepare electric conducting material slurry;
Described electric conducting material dispersion liquid is formed conductive layer in electric insulation stromal surface, forms the first composite diaphragm; Or described electric conducting material slurry is formed conductive layer in electric insulation stromal surface, form the second composite diaphragm; Wherein, the thickness of the described conductive layer of described first composite diaphragm or described second composite diaphragm is 5-50 μm;
Described first composite diaphragm is carried out dryness finalization after washing or by described second composite diaphragm, forms the 3rd composite diaphragm;
Described 3rd composite diaphragm is exerted pressure and carries out compaction treatment.
And, a kind of secondary cell, it barrier film comprising positive electrode, negative electrode and be arranged between positive electrode and negative electrode, the secondary cell composite diaphragm that described barrier film is above-mentioned secondary cell composite diaphragm or is prepared by the preparation method of above-mentioned secondary cell composite diaphragm.
Compared with prior art, secondary cell composite diaphragm of the present invention is combined in electric insulation substrate layer surface by electric conducting material being adopted the mode of Rotating fields, such conductive layer just fits tightly at electric insulation substrate layer surface, remain the good porosity of electric insulation matrix on the one hand, allow the infiltration of electrolyte and the diffusion of ion.On the other hand, conductive layer is closely stacking three-dimensional conductive network, and this structure can be tackled and be come off electrode material from current collector, and is adsorbed on conductive material surface; Because conductive layer self-conductive is good, can carry out current delivery with current collector, this just makes conductive layer play the effect similar with current collector, thus allow the electrode material be adsorbed on electric conducting material proceed discharge and recharge, effectively prevent battery from producing fast capacity decline because electrode material comes off, improve battery cycle life.In addition, electric insulation hypothallus meets the condition that common batteries barrier film should possess, and serves as insulating barrier, maceration electrolyte, provides ion diffuse path etc., also serves as the support base of conductive layer simultaneously, provides the mechanical strength needed for composite diaphragm.
The preparation method of above-mentioned secondary cell composite diaphragm can by the control to conductive layer, conductive layer is made effectively to be combined on electric insulation substrate layer surface, closely stacking three-dimensional conductive network, ensure the Stability Analysis of Structures of secondary cell composite diaphragm, thus effectively realize tackling the electrode material come off from current collector.Meanwhile, remain the good porosity of electric insulation matrix, allow the infiltration of electrolyte and the diffusion of ion.In addition, the method condition is easy to control, the stable performance of the secondary cell composite diaphragm of preparation, and its technique is simple, and production efficiency is high, can suitability for industrialized production, effectively reduces production cost.
Above-mentioned secondary cell is owing to adopting above-mentioned secondary cell composite diaphragm, and therefore, this secondary cell has excellent cycle life.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing:
Fig. 1 is the structural representation of embodiment of the present invention secondary cell composite diaphragm;
Fig. 2 is embodiment of the present invention secondary cell composite diaphragm preparation method flow chart;
Fig. 3 provides the button cell structural representation containing embodiment of the present invention secondary cell composite diaphragm for the embodiment of the present invention 1;
Fig. 4 is for providing the button cell of secondary cell composite diaphragm and common button cell capability retention curve chart containing the embodiment of the present invention 1; Wherein, Fig. 4 is a) button cell capability retention curve chart common in comparative example; Fig. 4 b) for providing the capability retention curve chart of the button cell of secondary cell composite diaphragm containing the embodiment of the present invention 1.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Example of the present invention provides a kind of effective secondary cell composite diaphragm realizing the electrode material that interception comes off from current collector, and its structure as shown in Figure 1.This secondary cell composite diaphragm comprises electric insulation hypothallus 1 and is combined in the conductive layer 2 on electric insulation hypothallus 1 surface.
Wherein, this conductive layer 2 adopts the mode of Rotating fields to be combined in electric insulation hypothallus 1 surface, and such conductive layer 2 just fits tightly at electric insulation substrate layer surface, remains the good porosity of electric insulation matrix on the one hand, allows the infiltration of electrolyte and the diffusion of ion.On the other hand, conductive layer is closely stacking three-dimensional conductive network, and this structure can be tackled and be come off electrode material from current collector, and is adsorbed on conductive material surface; Because conductive layer self-conductive is good, can carry out current delivery with current collector, this just makes conductive layer play the effect similar with current collector, thus allow the electrode material be adsorbed on electric conducting material proceed discharge and recharge, effectively prevent battery from producing fast capacity decline because electrode material comes off, improve battery cycle life.In addition, electric insulation hypothallus meets the condition that common batteries barrier film should possess, and serves as insulating barrier, maceration electrolyte, provides ion diffuse path etc., also serves as the support base of conductive layer simultaneously, provides the mechanical strength needed for composite diaphragm.
In addition, inventor finds in research process, when conductive layer 2 THICKNESS CONTROL is less than 5 μm, then cannot play the effect of tackling the electrode material come off; When conductive layer 2 THICKNESS CONTROL is greater than 50 μm, then can greatly increase barrier film integral thickness, expand both positive and negative polarity spacing, and then infringement battery fast charging and discharging ability.Therefore, in embodiment of the present invention secondary cell composite diaphragm, this conductive layer 2 thickness is 5-50 μm.In a preferred embodiment, this conductive layer 2 thickness is 20-30 μm.In certain embodiments, this conductive layer 2 thickness is 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm etc.
It is axiomatic that include electric conducting material in the material forming this conductive layer 2, this electric conducting material should be applicable to secondary cell.In one embodiment, at least one in graphite flake, carbon nano-tube, Graphene, carbon nano-fiber, nano carbon microsphere selected by the electric conducting material in this conductive layer 2.This electric conducting material selected not only has excellent electric conductivity, the more important thing is that it effectively can be stacked into three-dimensional conductive network at electric insulation hypothallus 1 intimate surface, effective interception to come off electrode material from current collector, meanwhile, electric insulation matrix 1 porosity preferably can also effectively be retained.
In order to provide the structural stability between conductive layer 2 and electric insulation hypothallus 1, in one embodiment, also binding agent is included in the material of this conductive layer 2.Inventor also finds in research process, the mass ratio of this binding agent and electric conducting material can be affected conductive layer 2 conductivity higher than 1:2, its electric conductivity is declined; When the mass ratio of this binding agent and electric conducting material then can affect structural stability between conduction 2 and electric insulation hypothallus 1 lower than 1:5, both are died down at bond strength, therefore, in one embodiment, the mass ratio of this binding agent and electric conducting material is 1:(2 ~ 5).In certain embodiments, the mass ratio of this binding agent and electric conducting material can be 1:2,1:3,1:4,1:5.
In one embodiment, this binding agent selects Kynoar, polytetrafluoroethylene etc.This binding agent selected effectively can strengthen conductive layer 2 and the steadiness of electric insulation hypothallus 1 surface conjunction, does not affect the electric conductivity of conductive layer 2 simultaneously.
On the basis of the various embodiments described above, this electric insulation hypothallus 1 meets the condition that common batteries barrier film should possess, serve as insulating barrier, maceration electrolyte, ion diffuse path etc. is provided, also serve as the support base of conductive layer simultaneously, the mechanical strength needed for composite diaphragm is provided.Therefore, electric insulation hypothallus 1 can select the barrier film of secondary cell routine.In one embodiment, this electric insulation hypothallus 1 selects commercial lithium ion battery polymer barrier film, fibreglass diaphragm or ordinary filter paper etc.In order to make between this electric insulation hypothallus 1 and conductive layer 2 structure more firm, this electric insulation hypothallus 1 choose with the electric conducting material kind in conductive layer 2 and prepare conductive layer 2 time solvent kind mate.In one embodiment, during using water as solvent, because water does not have wettability to commercial lithium ion battery polymer barrier film, then can not use this type of polymer class barrier film, fibreglass diaphragm or ordinary filter paper then successfully can filter out the electric conducting material in the aqueous solution.In another embodiment, because the pore diameter of fibreglass diaphragm and ordinary filter paper will be far longer than commercial polymers barrier film, thus they can not be used to filter sizes at nano level electric conducting material, as nano carbon microsphere, therefore, at least one in graphite flake, carbon nano-tube, Graphene, carbon nano-fiber selected by electric conducting material.
From the above, above-described embodiment secondary cell composite diaphragm is by the synergy of electric insulation hypothallus 1 with conductive layer 2, above-described embodiment secondary cell composite diaphragm is made to have the good porosity of electric insulation matrix, the three-dimensional conductive network that simultaneously conductive layer 2 is formed effectively can be tackled and be come off electrode material from current collector, and be adsorbed on conductive material surface, thus allow the electrode material be adsorbed on electric conducting material proceed discharge and recharge, effectively prevent battery from producing fast capacity decline because electrode material comes off, improve battery cycle life.
Correspondingly, the embodiment of the present invention additionally provides a kind of preparation method of secondary cell composite diaphragm mentioned above.Preparation method's technological process of this secondary cell composite diaphragm refers to Fig. 2, and please consult Fig. 1, it comprises the steps: simultaneously
Step S01. preparation contains dispersion liquid or the slurry of electric conducting material:
Be mixed with electric conducting material dispersion liquid by electric conducting material and surfactant-dispersed to liquid solvent, or electric conducting material and binding agent are added in solvent prepare electric conducting material slurry;
Step S02. by containing the dispersion liquid of electric conducting material or slurry at electric insulation stromal surface conductive layer:
The electric conducting material dispersion liquid prepared in step S01 is formed conductive layer 2 on the surface in electric insulation matrix 1, forms the first composite diaphragm; Or the electric conducting material slurry prepared in step S01 is formed conductive layer 2 on the surface in electric insulation matrix 1, form the second composite diaphragm;
Step S03. is by composite diaphragm dryness finalization:
The second composite diaphragm that the first composite diaphragm prepared by step S02 is prepared after washing or by step S02 carries out dryness finalization, forms the 3rd composite diaphragm;
Composite diaphragm compaction treatment after drying is shaped by step S04.:
The 3rd composite diaphragm prepared by step S03 is exerted pressure and is carried out compaction treatment.
Particularly, in above-mentioned steps S01, when electric conducting material is prepared dispersion liquid, this surfactant prevents from reuniting due to the Electrostatic Absorption of electric conducting material, thus cause electric conducting material to disperse uneven technical problem.In one embodiment, the mass ratio of electric conducting material and surfactant is (1 ~ 10): 1, in certain embodiments, the mass ratio of this electric conducting material and surfactant is 1:1,2:1,3:1,4:1,5:1,6:1,7:1,8:1,9:1,10:1 etc.Both effectively avoid electric conducting material to reunite at mass-energy density within the scope of this, effectively can prevent again surfactant remaining in finished product, thus affect the electric conductivity etc. of conductive layer.
Reunite to effectively prevent electric conducting material, in one embodiment, the mixture of any one or more in the high molecular type surfactant such as PVP, polyethylene glycol, softex kw plasma type surfactant selected by this surfactant.
In addition, in the dispersion liquid of preparation, the mass percentage concentration of this electric conducting material is 0.1-1%, is preferably 0.1-0.5%.The dispersion liquid of this percentage concentration can coordinate dispersant effectively to prevent electric conducting material from reuniting and sedimentation, effectively can ensure that again electric conducting material builds up the conductive layer 2 of three-dimensional conductive network at electric insulation stromal surface compact reactor simultaneously.
In one embodiment, the liquid solvent for preparing dispersion liquid selects one or more the mixed solvent in water, ethanol, acetone, ethylene glycol, nitrogen methyl pyrrolidone etc.
When electric conducting material is prepared slurry, in one embodiment, be 1:(2 ~ 5 by electric conducting material and binding agent according to mass ratio) ratio carry out adding in solvent and carry out batch mixing dispersion treatment, form uniform slurry.In one embodiment, as described above, it selects Kynoar, polytetrafluoroethylene etc. to the kind selected by this binding agent.In one embodiment, the solvent for preparing slurry can select the solution that effectively can dissolve binding agent, and as in one embodiment, this solution selects nitrogen methyl pyrrolidone etc.In addition, the concentration of this slurry can adjust according to the requirement of actual production.
In this step S01, no matter be preparation dispersion liquid or slurry, in one embodiment, as described above, it selects at least one in graphite flake, carbon nano-tube, Graphene, carbon nano-fiber, nano carbon microsphere to the material that this conductive agent is selected.
In above-mentioned steps S02, when adopting dispersion liquid to form conductive layer 2, the method that electric conducting material dispersion liquid forms conductive layer 2 on the surface in electric insulation matrix 1 can adopt the methods such as filtration or sedimentation.Wherein, filter method formed conductive layer 2 time, be using electric insulation matrix 1 as filter membrane, put dispersion liquid and flow through electric insulation matrix 1 with the flow velocity of 0.1 ~ 2.5cm/min, thus electric conducting material is trapped and electric insulation matrix 1 surface formed conductive layer 2.
When sedimentation method forms conductive layer 2, be electric insulation matrix 1 is fixedly laid in horizontal positioned have in the container of flat bottom, dispersion liquid is poured in container, leave standstill 10 ~ 60min, be deposited to behind electric insulation matrix 1 surface until electric conducting material, remove surplus solution, thus form conductive layer 2 on electric insulation matrix 1 surface.
When adopting slurry to form conductive layer 2, directly slurry can be carried out coating film forming on electric insulation matrix 1 surface, as adopted the modes such as brushing, spraying.In order to obtain high-quality conductive layer 2, in one embodiment, by the electric conducting material slurry in above-mentioned steps S01, the mass concentration of this electric conducting material controls 0.1% ~ 0.2%.
In this step S02, no matter adopt dispersion liquid to form conductive layer 2 or adopt slurry to form conductive layer 2.In one embodiment, should to the control of process conditions, by formed conductive layer 2 THICKNESS CONTROL between 5-50 μm.Preferably control between 20-30 μm.
In above-mentioned steps S03, the object of the first composite diaphragm through washing prepared step S02 removes the solvent and surfactant that remain in the first composite diaphragm.In order to effectively removing remains in solvent and surfactant in the first composite diaphragm, in one embodiment, washing adopts washing agent to process, and in certain embodiments, this washing agent is selected the one in distilled water, ethanol, acetone or adopted and two or morely to process respectively.In addition, when selecting washing agent, surfactant, the liquid solvent solubility property relative to washing agent should be considered.As such as surfactant PVP is insoluble to acetone, then use PVP as during surfactant can not with acetone as washing agent.Through carrying out washing treatment, the solvent in the first composite diaphragm that removing is residual and surfactant, ensure the electric conductivity of conductive layer 2 and the stability of closely stacking three-dimensional conductive network.The first composite diaphragm after carrying out washing treatment, in drying process, removes washing agent.
In this step S03, because the second composite diaphragm adopts slurry to carry out coating to be formed, therefore, directly this second composite diaphragm is carried out drying process except desolventizing.
In order to ensure three-dimensional conductive network in conductive layer 2 stability, improve the quality of this conductive layer 2, in one embodiment, the process conditions of this dryness finalization are 40 ~ 60 DEG C of constant pressure and dry 24 ~ 48h, or 20 ~ 60 DEG C of vacuumize 6 ~ 12h.Baking temperature is no more than 60 DEG C.
In above-mentioned steps S04, be the surface making conductive layer 2 closely and be firmly combined in electric insulation hypothallus 1 to the object of the 3rd composite diaphragm compaction treatment.Therefore, in one embodiment, the pressure of exerting pressure described 3rd composite diaphragm being carried out to compaction treatment is 5 ~ 30MPa, is preferably 10-20MP.The time of exerting pressure is 20 ~ 60S.By this compaction treatment of these process conditions, make this conductive layer 2 closely and be firmly combined on the basis on the surface of electric insulation hypothallus 1, making conductive layer 2 remain the good porosity of electric insulation matrix and the specific three-dimensional conductive network of tight stacking formation.
Therefore, the preparation method of above-mentioned secondary cell composite diaphragm can control passing through conductive layer formation method, conductive layer is made effectively to be combined on electric insulation substrate layer surface, closely stacking three-dimensional conductive network, ensure the Stability Analysis of Structures of secondary cell composite diaphragm, thus effectively realize tackling the electrode material come off from current collector.Meanwhile, remain the good porosity of electric insulation matrix, allow the infiltration of electrolyte and the diffusion of ion.In addition, the method condition is easy to control, the stable performance of the secondary cell composite diaphragm of preparation, and its technique is simple, and production efficiency is high, can suitability for industrialized production, effectively reduces production cost.
Correspondingly, on the basis of secondary cell composite diaphragm mentioned above and preparation method thereof, the embodiment of the present invention further provides a kind of secondary cell, and this secondary cell comprises secondary cell composite diaphragm mentioned above.It is axiomatic that this secondary cell also comprises the necessary miscellaneous part of lithium ion battery, as positive pole, negative pole, electrolyte, because this miscellaneous part is conventional, therefore, miscellaneous part is not repeated at this.In one embodiment, this secondary cell is lithium ion battery.
Like this, this secondary cell is due to containing above-mentioned secondary cell composite diaphragm, therefore, when expand in process at deintercalate lithium ions of the electrode material of secondary cell come off time, this secondary cell composite diaphragm effectively to electrode material interception, and can be adsorbed on the surface of conductive layer 2, thus make electrode material together with conductive layer 2, allow and can be proceeded discharge and recharge by adsorption electrode material, effectively prevent battery generation fast capacity from failing, improve battery cycle life.
This secondary cell is owing to having long battery cycle life.Therefore, this secondary cell such as lithium ion battery can be applied in such as communication equipment, electric automobile, but is not limited only to communication equipment, electric automobile, can also with in other field.
The aspects such as above-mentioned secondary cell composite diaphragm and preparation method thereof, secondary cell performance are illustrated below by way of multiple embodiment.
Embodiment 1
A kind of secondary cell composite diaphragm and preparation method thereof.The structure of this secondary cell composite diaphragm is as shown in Figure 1.It conductive layer 2 comprising electric insulation hypothallus 1 and be combined in electric insulation hypothallus 1 surface.Wherein, the material selection Celgard 2400 type lithium ion battery polymer barrier film of this electric insulation hypothallus 1; The thickness of conductive layer 2 is 20 μm, and it comprises carbon nano-tube as electric conducting material.
Preparation method is as follows for this secondary cell composite diaphragm:
S11. electric conducting material and PVP are added in absolute ethyl alcohol according to the ratio of mass ratio 5:1, fully disperse, be mixed with uniform electric conducting material dispersion liquid;
S12. adopt the mode of filtering to flow through electric insulation matrix 1 with the flow velocity of 0.2cm/min the electric conducting material dispersion liquid prepared in step S11, electric conducting material is trapped on electric insulation matrix 1 surface and forms uniform conductive material layer 2, obtained composite diaphragm;
S13. the composite diaphragm prepared by step S12 adopts the rear 50 DEG C of vacuumize 48h of acetone washing to shape, residual surfactant and solvent in removing composite diaphragm;
S14. exerted pressure by the composite diaphragm of step S13 dryness finalization and carry out compaction treatment and obtain secondary cell composite diaphragm, wherein pressure setting is 10MPa, and time controling is 30S.
Embodiment 2
A kind of secondary cell composite diaphragm and preparation method thereof.The structure of this secondary cell composite diaphragm is as shown in Figure 1.It conductive layer 2 comprising electric insulation hypothallus 1 and be combined in electric insulation hypothallus 1 surface.Wherein, material selection Celgard 2400 membrane for polymer of this electric insulation hypothallus 1; The thickness of conductive layer 2 is 30 μm, and it comprises Graphene as electric conducting material and polyvinylidene fluoride as binding agent, and the mass ratio of this electric conducting material and binding agent is 4:1.
Preparation method is as follows for this secondary cell composite diaphragm:
S21. electric conducting material and binding agent are added in nitrogen methyl pyrrolidone according to the ratio of mass ratio 4:1, carry out abundant mixing treatment, be mixed with uniform electric conducting material slurry;
S22. the electric conducting material slurry prepared in step S21 is coated in the surface of electric insulation matrix 1, forms the uniform conductive layer 2 of thickness;
S23. the composite diaphragm prepared by step S22 is in the dry 24h sizing of normal pressure 60 DEG C;
S24. exerted pressure by the composite diaphragm of step S23 dryness finalization and carry out compaction treatment and obtain secondary cell composite diaphragm, wherein pressure setting is 10MPa, and time controling is 30S.
Embodiment 3
A kind of secondary cell composite diaphragm and preparation method thereof.The structure of this secondary cell composite diaphragm is as shown in Figure 1.It conductive layer 2 comprising electric insulation hypothallus 1 and be combined in electric insulation hypothallus 1 surface.Wherein, the material selection cellulosic filter paper of this electric insulation hypothallus 1; The thickness of conductive layer 2 is 30 μm, and it comprises graphite flake as electric conducting material.
Preparation method is as follows for this secondary cell composite diaphragm:
S31. electric conducting material and PVP are joined in distilled water according to the mass ratio of 5:1, and fully dispersion forms electric conducting material dispersion liquid;
S32. cellulosic filter paper is fixed tiling to flat bottom of gullet and by tank water placing flat; Then the dispersion liquid that step S31 prepares is poured in flat tank, after leaving standstill 24h, remove the solution in tank, form uniform conductive layer 2 on dielectric substrate layer 1 surface;
S33. the composite diaphragm prepared by step S32 is shaped in 50 DEG C of vacuumize 48h;
S34. exerted pressure by the composite diaphragm of step S33 dryness finalization and carry out compaction treatment and obtain secondary cell composite diaphragm, wherein pressure setting is 15MPa, and time controling is 40S.
Embodiment 4
A kind of secondary cell composite diaphragm and preparation method thereof.The structure of this secondary cell composite diaphragm is as shown in Figure 1.It conductive layer 2 comprising electric insulation hypothallus 1 and be combined in electric insulation hypothallus 1 surface.Wherein, the material selection Celgard 2400 type lithium ion battery polymer barrier film of this electric insulation hypothallus 1; The thickness of conductive layer 2 is 5 μm, and it comprises nano carbon microsphere as electric conducting material.
Preparation method is as follows for this secondary cell composite diaphragm:
S41. electric conducting material and softex kw ionic surfactant are added in ethylene glycol according to the ratio of mass ratio 10:1, fully disperse, be mixed with uniform electric conducting material dispersion liquid;
S42. adopt the mode of filtering to flow through electric insulation matrix 1 with the flow velocity of 2.5cm/min the electric conducting material dispersion liquid prepared in step S41, electric conducting material is trapped on electric insulation matrix 1 surface and forms uniform conductive material layer 2, obtained composite diaphragm;
S43. the composite diaphragm prepared by step S42 is shaped in 40 DEG C of vacuumize 48h after adopting acetone washing, residual surfactant and solvent in removing composite diaphragm;
S44. exerted pressure by the composite diaphragm of step S43 dryness finalization and carry out compaction treatment and obtain secondary cell composite diaphragm, wherein pressure setting is 30MPa, and time controling is 20S.
Embodiment 5
A kind of secondary cell composite diaphragm and preparation method thereof.The structure of this secondary cell composite diaphragm is as shown in Figure 1.It conductive layer 2 comprising electric insulation hypothallus 1 and be combined in electric insulation hypothallus 1 surface.Wherein, the material selection fibreglass diaphragm of this electric insulation hypothallus 1; The thickness of conductive layer 2 is 50 μm, and it comprises carbon nano-fiber and the graphite flake hybrid conductive material according to quality 1:1.
Preparation method is as follows for this secondary cell composite diaphragm:
S51. electric conducting material and softex kw ionic surfactant are added in ethylene glycol according to the ratio of mass ratio 2:1, fully disperse, be mixed with uniform electric conducting material dispersion liquid;
S52. adopt the mode of filtering to flow through electric insulation matrix 1 with the flow velocity of 0.2cm/min the electric conducting material dispersion liquid prepared in step S51, electric conducting material is trapped on electric insulation matrix 1 surface and forms uniform conductive material layer 2, obtained composite diaphragm;
S53. the composite diaphragm prepared by step S52 is shaped in 60 DEG C of vacuumize 30h after adopting acetone washing, residual surfactant and solvent in removing composite diaphragm;
S54. exerted pressure by the composite diaphragm of step S53 dryness finalization and carry out compaction treatment and obtain secondary cell composite diaphragm, wherein pressure setting is 5MPa, and time controling is 30S.
Secondary cell embodiment
By the secondary cell composite diaphragm difference fastening lithium ionic cell assembling conveniently provided in the various embodiments described above, the fastening lithium ionic cell structure be assembled into as shown in Figure 3.Secondary cell composite diaphragm is layered between the electrode of fastening lithium ionic cell and lithium sheet, wherein, electrode comprises current collector 4 and is combined in the electrode material layer 3 on current collector 4 surface, the conductive layer 2 of secondary cell composite diaphragm is stacked with the electrode material layer 3 of electrode, and electric insulation hypothallus 1 is stacked with lithium sheet 5.
Secondary cell comparative example
The conventional button lithium battery adopting common diaphragm is provided.
Performance test:
The button lithium battery of the common diaphragm in each button lithium battery prepared in secondary cell embodiment and comparative example is carried out respectively the test experiments of capability retention.
Wherein, the capability retention test result of the button lithium battery adopting the secondary cell composite diaphragm provided in embodiment 1 to prepare is as Fig. 4 b) shown in.In comparative example the button lithium battery of common diaphragm capability retention test result as Fig. 4 a) shown in.Comparison diagram 4a) and Fig. 4 b), in identical condition, the button lithium battery that the embodiment of the present invention provides has obvious capability retention in charge and discharge process.
By test, button lithium battery test result prepared by the secondary cell composite diaphragm adopting other embodiments to provide and Fig. 4 a) similar.
It can thus be appreciated that, secondary cell composite diaphragm prepared by the present invention is on the basis with advantages such as good porosity and mechanical strengths, its effect by conductive layer 2 interception to come off electrode material from current collector, thus allow electrode material proceed discharge and recharge, effectively improve secondary cell cycle life.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a secondary cell composite diaphragm, it conductive layer comprising electric insulation hypothallus and be combined in described electric insulation substrate layer surface, described conductive layer includes electric conducting material, and the thickness of described conductive layer is 5-50 μm.
2. secondary cell composite diaphragm according to claim 1, is characterized in that: the thickness of described conductive layer is 20 ~ 30 μm.
3. secondary cell composite diaphragm according to claim 1, is characterized in that: described conductive layer is also containing binding agent, and described binding agent and described electric conducting material mass ratio are 1:(2 ~ 5).
4., according to the arbitrary described secondary cell composite diaphragm of claims 1 to 3, it is characterized in that: described electric conducting material is selected from least one in graphite flake, carbon nano-tube, Graphene, carbon nano-fiber, nano carbon microsphere.
5., according to the arbitrary described secondary cell composite diaphragm of claims 1 to 3, it is characterized in that: described electric insulation hypothallus material is selected from any one in lithium ion battery polymer barrier film, fibreglass diaphragm, filter paper.
6. a preparation method for secondary cell composite diaphragm, comprises the steps:
Be mixed with electric conducting material dispersion liquid by electric conducting material and surfactant-dispersed to liquid solvent, or electric conducting material and binding agent are added in solvent prepare electric conducting material slurry;
Described electric conducting material dispersion liquid is formed conductive layer in electric insulation stromal surface, forms the first composite diaphragm; Or described electric conducting material slurry is formed conductive layer in electric insulation stromal surface, form the second composite diaphragm; Wherein, the thickness of the described conductive layer of described first composite diaphragm or described second composite diaphragm is 5-50 μm;
Described first composite diaphragm is carried out dryness finalization after washing or by described second composite diaphragm, forms the 3rd composite diaphragm;
Described 3rd composite diaphragm is exerted pressure and carries out compaction treatment.
7. the preparation method of secondary cell composite diaphragm according to claim 7, is characterized in that: the mass ratio of described electric conducting material and surfactant is (1 ~ 10): 1; And/or
Described electric conducting material and binding agent mass ratio be (2 ~ 5): 1; And/or
The mass concentration of the electric conducting material in described electric conducting material slurry is 0.1% ~ 0.2%.
8. the preparation method of the secondary cell composite diaphragm according to claim 6 or 7, is characterized in that: the thickness of the described conductive layer of described first composite diaphragm or described second composite diaphragm is 20 ~ 30 μm; And/or
The mixture of any one or more in PVP, polyethylene glycol polymer type surfactant, softex kw ionic surfactant selected by described surfactant; And/or
In the step of preparation first composite diaphragm, using described electric insulation matrix as filter membrane, described electric conducting material dispersion liquid is flow through electric insulation matrix with the flow velocity of 0.1 ~ 2.5cm/min, make described electric conducting material form conductive layer in described electric insulation stromal surface.
9. the preparation method of the secondary cell composite diaphragm according to claim 6 or 7, is characterized in that: the pressure of exerting pressure described 3rd composite diaphragm being carried out to compaction treatment is 5 ~ 30MPa, and the time is 10 ~ 100S.
10. a secondary cell, it barrier film comprising positive electrode, negative electrode and be arranged between positive electrode and negative electrode, the secondary cell composite diaphragm that described barrier film is the arbitrary described secondary cell composite diaphragm of Claims 1 to 5 or is prepared by the preparation method of the arbitrary described secondary cell composite diaphragm of claim 6 ~ 9.
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| CN106057493A (en) * | 2016-05-18 | 2016-10-26 | 湖北大学 | Method for preparing super capacitor diaphragm |
| CN106876634A (en) * | 2017-03-09 | 2017-06-20 | 清华大学 | Composite diaphragm and preparation method thereof, and lithium ion battery |
| CN112993486A (en) * | 2021-02-09 | 2021-06-18 | 北京理工大学 | Method for improving multiplying power and cycle life of silicon-based negative electrode battery |
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