CN109659565A - Composite current collector and preparation method thereof, electrode and lithium ion battery - Google Patents
Composite current collector and preparation method thereof, electrode and lithium ion battery Download PDFInfo
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- CN109659565A CN109659565A CN201811590087.7A CN201811590087A CN109659565A CN 109659565 A CN109659565 A CN 109659565A CN 201811590087 A CN201811590087 A CN 201811590087A CN 109659565 A CN109659565 A CN 109659565A
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- current collector
- composite current
- collector
- lithium ion
- bismuth
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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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
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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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 present invention relates to a kind of composite current collector and preparation method thereof, electrode and lithium ion batteries, and wherein composite current collector includes collector and the surface covering for being formed in collector, and surface covering includes nanometer bismuth, nano bismuth oxide, binder and conductive agent.Nanometer bismuth in the surface covering of above-mentioned composite current collector is nanometer scale, can increase the contact area of the active material in collector and active material layer, and then reduce interface internal resistance, to improve the stability of battery capacity；And the fusing point of nanometer bismuth is low, can the fusing when lithium ion battery is heated, contact of the active material with collector is cut off, so that cutting off conductive path avoids further thermal runaway.The compatibility of nanometer bismuth and nano bismuth oxide is good, nano bismuth oxide in composite current collector with fire retardation is when lithium ion battery heating temperature increases, it can inhibit cells burst with nanometer bismuth cooperative achievement, play the role of preventing lithium ion battery explosion, and then improve the security performance of battery.
Description
Technical field
It is special than being to be related to a kind of composite current collector and preparation method thereof, electrode and lithium the present invention relates to battery technology field
Ion battery.
Background technique
With the fast development of new energy industry, the requirement to electrochemical apparatus is also increasingly improved.On the one hand more demanding
The chemical properties such as energy density, fast charging and discharging；On the other hand higher security performance is pursued.Collector is lithium-ion electric
Important component part in pond, refers to the mechanics carrier of carrying positive or negative pole active material, while can provide and move for electronics
Mobile Communication road.Current affluxion body in lithium ion batteries is mostly copper foil and aluminium foil, the battery capacity based on lithium ion battery made from this
Stability is to be improved；In addition, current lithium ion battery there is a problem of explosive in an environment of high temperature, therefore its environment is deposited
The temperature put is preferably at 35 DEG C or less.
Summary of the invention
Based on this, it is necessary to provide a kind of collection of battery capacity stability and security performance that can be improved lithium ion battery
Fluid.
One aspect of the present invention provides a kind of composite current collector, including collector and is formed in the collector
Surface covering, the surface covering include nanometer bismuth, nano bismuth oxide, binder and conductive agent.
The nanometer bismuth, the nano bismuth oxide, the binder and the conductive agent in one of the embodiments,
Mass ratio is (6~8): (0.5~1.5): (0.1~0.5): (0.1~0.5).
The partial size of the nanometer bismuth is 5nm~100nm in one of the embodiments,；The partial size of the nano bismuth oxide
For 10nm~100nm.Preferably, the specific surface area of nanometer bismuth and nano bismuth oxide is 1~50m2/g。
The thickness of the surface covering is no more than 2 microns in one of the embodiments,.
The binder is selected from butadiene-styrene rubber, acrylic resin, carboxymethyl cellulose, gathers in one of the embodiments,
At least one of tetrafluoroethene lotion, Kynoar and polyvinyl alcohol；
The conductive agent is in carbon black, acetylene black, carbon fiber, carbon nanotube, graphene, Ketjen black, SP and KS-6
It is at least one.
The collector is selected from aluminium foil, nickel foam, nickel foil, nickel screen, copper mesh, copper foil, stainless in one of the embodiments,
In steel mesh, stainless steel Punching steel strip, stainless steel foil, titanium foil, titanium net, lead foil, lead cloth, graphitization carbon cloth and graphene cloth material
It is at least one.
Another aspect of the present invention provides a kind of preparation method of composite current collector, comprising the following steps:
Nanometer bismuth, nano bismuth oxide, binder and conductive agent are mixed in a solvent, obtain slurry；
The slurry is coated on to the surface of collector, drying obtains composite current collector.
Another aspect of the present invention provides a kind of electrode, including composite current collector described in any of the above embodiments and shape
Active material layer on the surface covering of composite current collector described in Cheng Yu.
The electrode is lithium ion battery electrode in one of the embodiments,；The electrode is anode, the activity
Material layer contains tertiary cathode material；Or the electrode is cathode, the active material layer contains graphite cathode material.
Another aspect of the present invention, provides a kind of lithium ion battery, in the anode and cathode of the lithium ion battery
At least one be electrode described in any of the above embodiments.
Above-mentioned composite current collector can be used for lithium ion battery, and the nanometer bismuth in the surface covering of composite current collector is nanometer amount
Grade has biggish specific surface area, can increase the contact area of the active material in collector and active material layer, and then subtracts
Small interface internal resistance, to improve the cycle performance of battery and the stability of battery capacity；And the fusing point of nanometer bismuth is low, it can be in lithium
Ion battery fuses when heated, cuts off contact of the active material with collector, to cut off conductive path, avoids further heat mistake
Control.At the same time, the compatibility of nanometer bismuth and nano bismuth oxide is good, with fire retardation in the surface covering of composite current collector
Nano bismuth oxide can inhibit cells burst with nanometer bismuth cooperative achievement, play and prevent when lithium ion battery heating temperature increases
The effect of lithium ion battery explosion, and then improve the security performance of battery.
In addition, the superconductivity of bismuth can reduce the internal resistance of cell, above-mentioned composite current collector also has preferable at low temperatures
Battery capacity stability.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of composite current collector made from embodiment 1；
Fig. 2 is the loop test performance map of lithium ion battery made from embodiment 6 and comparative example 1.
Specific embodiment
To facilitate the understanding of the present invention, below will to invention is more fully described, and give it is of the invention compared with
Good embodiment.But the invention can be realized in many different forms, however it is not limited to embodiment described herein.Phase
Instead, purpose of providing these embodiments is makes the disclosure of the present invention more thorough and comprehensive.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases
Any and all combinations of the listed item of pass.
An embodiment of the present invention provides a kind of composite current collector, applies including collector and the surface for being formed in collector
Layer, surface covering includes nanometer bismuth, nano bismuth oxide, binder and conductive agent.
The partial size of nanometer bismuth is 5nm~100nm in one of the embodiments,；The partial size of nano bismuth oxide be 10nm~
100nm.Preferably, the specific surface area of nanometer bismuth and nano bismuth oxide is 1~50m2/g。
The thickness of surface covering is no more than 2 microns in one of the embodiments,.
Binder includes but is not limited to butadiene-styrene rubber, acrylic resin, carboxymethyl cellulose in one of the embodiments,
At least one of element, ptfe emulsion, Kynoar and polyvinyl alcohol.Conductive agent includes but is not limited to carbon black, second
At least one of acetylene black, carbon fiber, carbon nanotube, graphene, Ketjen black, SP and KS-6.Collector includes but is not limited to aluminium
Foil, nickel foam, nickel foil, nickel screen, copper mesh, copper foil, stainless (steel) wire, stainless steel Punching steel strip, stainless steel foil, titanium foil, titanium net, lead
Foil, lead cloth, graphitization at least one of carbon cloth and graphene cloth material.
Above-mentioned composite current collector can be used for lithium ion battery, and the nanometer bismuth in the surface covering of composite current collector is nanometer amount
Grade has biggish specific surface area, can increase the contact area of the active material in collector and active material layer, and then subtracts
Small interface internal resistance, to improve the cycle performance of battery and the stability of battery capacity；And the fusing point of nanometer bismuth is low, it can be in lithium
Ion battery fuses when heated, cuts off contact of the active material with collector, to cut off conductive path, avoids further heat mistake
Control.At the same time, the compatibility of nanometer bismuth and nano bismuth oxide is good, with fire retardation in the surface covering of composite current collector
Nano bismuth oxide can inhibit cells burst with nanometer bismuth cooperative achievement, play and prevent when lithium ion battery heating temperature increases
The effect of lithium ion battery explosion, and then improve the security performance of battery.
Further, since the superconductivity of bismuth can reduce the internal resistance of cell, above-mentioned composite current collector also has at low temperatures
There is preferable battery capacity stability.
The mass ratio of nanometer bismuth, nano bismuth oxide, binder and conductive agent is (6~8) in one of the embodiments:
(0.5~1.5): (0.1~0.5): (0.1~0.5)；The proportion for controlling nanometer bismuth, nano bismuth oxide, binder and conductive agent can
Further increase battery capacity stability and security performance.
An embodiment of the present invention provides a kind of preparation method of any of the above-described kind of composite current collector, includes the following steps
S1~S2.
Step S1: nanometer bismuth, nano bismuth oxide, binder and conductive agent are mixed in a solvent, obtain slurry.
According to a kind of above-mentioned component offer raw material of the surface covering of composite current collector.Such as one embodiment wherein
In, nanometer bismuth, nano bismuth oxide, binder and conductive agent mass ratio be (6~8): (0.5~1.5): (0.1~0.5):
(0.1~0.5).
Wherein, solvent is preferably organic solvent, for example, N-Methyl pyrrolidone (NMP), DMF, ethyl alcohol, ethylene glycol, methanol,
Isopropanol etc..
It is understood that nanometer bismuth can react to obtain by soluble bismuth salt and reducing agent.Specifically, such as bismuth nitrate and boron hydrogen
Change sodium to react to obtain a nanometer bismuth.And China bismuth source is abundant, and using reactant concentration required by this method manufacture nanometer bismuth compared with
It is low, it is low in cost.
Slurry: being coated on the surface of collector by step S2, and drying obtains composite current collector.
Further, the condition of drying is that drying to constant weight in 80~120 DEG C of baking ovens.
The preparation method of above-mentioned composite current collector is easy to operate, is suitable for large-scale production and application；Compared to conventionally employedization
It learns vapour deposition process and the direct clad type of graphene is grown on copper foil surface to improve the high rate performance of battery and cycle life
Method, the preparation method condition of the above-mentioned composite current collector of the present invention is simply easily achieved, low for equipment requirements；And use nanometer
Bismuth and nano bismuth oxide make raw material, compared to the method using graphene and carbon nanotube, have the advantages that low in cost.
An embodiment of the present invention provides a kind of electrode, composite current collector including any of the above-described and is formed in compound
Active material layer on the surface covering of collector.
Above-mentioned electrode is lithium ion battery electrode in one of the embodiments,.
Further, above-mentioned electrode is anode, and active material layer contains tertiary cathode material, for providing lithium ion.Into
One step, tertiary cathode material therein can be NCM (nickel cobalt manganese) or NCA (nickel cobalt aluminium) etc., then using conventional method multiple
Anode active material layer is formed on intersection fluid.It specifically, can be by tertiary cathode material, binder and conductive agent in solvent
Anode sizing agent is made in middle mixing；Anode sizing agent is coated on composite current collector again, drying.
In another embodiment, above-mentioned electrode is cathode, and active material layer contains graphite cathode material, can be total to embedding lithium
Ion.Specifically, graphite, binder and conductive agent can be mixed in a solvent, negative electrode slurry is made；Negative electrode slurry is coated again
On composite current collector, drying.
Further, the conductive agent in anode sizing agent or negative electrode slurry be selected from carbon black, acetylene black, carbon fiber, carbon nanotube,
At least one of graphene, Ketjen black, SP, KS-6.Binder be selected from butadiene-styrene rubber, acrylic resin, carboxymethyl cellulose,
At least one of Kynoar, polyvinyl alcohol.
An embodiment of the present invention provides a kind of lithium ion battery, anode and at least one in cathode of lithium ion battery
Kind is the electrode of any of the above-described.
It is in one of the embodiments, the electrode of any of the above-described in the anode and cathode of lithium ion battery, i.e.,
It is made of above-mentioned composite current collector.Other preparation methods are all made of industry conventional method.
The lithium ion battery, using above-mentioned electrode, the cycle performance and security performance of battery are obviously improved.
The following are specific embodiments.
Below by embodiment, the present invention will be further described, but embodiment is not intended to limit protection scope of the present invention.
The preparation of 1 composite current collector of embodiment
(1) 0.01M bismuth nitrate solution and 0.01M sodium borohydride solution are prepared respectively；
(2) molar ratio for pressing sodium borohydride and bismuth nitrate 3:1, sodium borohydride is added drop-wise in bismuth nitrate solution, is dripped
Continue to stir 5min, revolving speed 1000rpm after, after product is washed with deionized, is dried to perseverance in 100 DEG C of drying boxes
Weight, prepares a nanometer bismuth.
(3) nanometer bismuth, nano bismuth oxide, binder, conductive agent are pressed into the mass ratio of 8.5:1.0:0.4:0.1 in a solvent
Mixing, obtains the slurry of bismuth containing nanometer and nano bismuth oxide.Slurry is coated in copper foil material surface again, is dried in 90 DEG C of baking ovens
To constant weight, composite current collector is obtained.Its coating thickness is less than 2 microns.Wherein, binder is ptfe emulsion, conductive
Agent is SP.The structural schematic diagram of composite current collector obtained is as shown in Figure 1, the surface of copper foil 101 is coated with bismuth containing nanometer and receives
The surface covering 102 of rice bismuth oxide.
The step of embodiment 2 prepares composite current collector is substantially the same manner as Example 1, the difference is that in step (3)
Nanometer bismuth, nano bismuth oxide, binder, conductive agent mass ratio be 6:1.5:0.5:0.5；Binder is butadiene-styrene latex and carboxylic first
Base sodium cellulosate conductive agent is acetylene black.
The step of embodiment 3 prepares composite current collector is substantially the same manner as Example 1, the difference is that in step (3)
Nanometer bismuth, nano bismuth oxide, binder, conductive agent mass ratio be 8:0.5:0.1:0.4；Binder is Kynoar, is led
Electric agent is carbon nanotube.
The step of embodiment 4 prepares composite current collector is substantially the same manner as Example 1, the difference is that in step (3)
Nanometer bismuth, nano bismuth oxide, binder, conductive agent mass ratio be 7:1:0.4:0.1；Binder is polyethylene alfin, conductive
Agent is carbon black.
Above embodiments 1~4 are the preparation embodiment of composite current collector；Embodiment 5~8 is that the preparation of lithium ion battery is real
Apply example.
The preparation of 5 lithium ion battery of embodiment
(1) ternary material NCM is chosen as anode, after it is mixed in nmp solvent with binder and conductive agent, is prepared
Anode sizing agent out；Anode sizing agent is coated on the resulting composite current collector of embodiment 1 again, then in 120 DEG C of vacuum ovens
Middle drying, obtains anode pole piece.
(2) graphite is chosen as negative electrode material, after it is mixed in ethylene glycol solvent with binder and conductive agent, is prepared
Negative electrode slurry out；Negative electrode slurry is coated on the resulting composite current collector of embodiment 1 again, then in 120 DEG C of vacuum ovens
Middle drying, obtains cathode pole piece.
(3) above-mentioned anode pole piece, cathode pole piece, diaphragm and lithium-ion electrolyte are assembled into lithium ion battery.
The step of embodiment 6~8 prepares lithium ion battery is substantially the same manner as Example 5, the difference is that step (1) and
The composite current collector used in step (2) is respectively composite current collector made from embodiment 2~4.
The preparation of 1 lithium ion battery of comparative example
The step of comparative example 1 prepares lithium ion battery is substantially the same manner as Example 5, the difference is that step (1) and step
Suddenly the composite current collector used in (2) is without the copper foil material coated by nanometer bismuth and nano bismuth oxide surface.
As shown in Fig. 2, wherein abscissa is the cycle-index (cycle number) of test, ordinate is remaining capacity
(SOC), embodiment 6 uses the lithium ion battery of composite current collector modified made from embodiment 2, at room temperature with the electric current of 1C
After carrying out loop test 800 times, capacity remains at 91.7% or so；The lithium ion battery of comparative example 1 is using non-modified
Copper foil material, after being carried out loop test 800 times with the electric current of 1C at room temperature, capacity retention ratio is then 80% or so.Other realities
Example also test loop performance in the same way is applied, is obtained after being carried out loop test 800 times with the electric current of 1C at room temperature
Capacity retention ratio, as shown in table 1.
Table 1
| Group | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Comparative example 1 |
| Capacity retention ratio | 88.7 | 91.7 | 90.3 | 91.1 | 83.285 |
Lithium ion battery made from above-described embodiment 5~8 and comparative example 1 is carried out overcharging experiment, concrete operations are as follows: first
By battery core with 1C electric current constant-current discharge to 3.0V, 10min is stood；Then with 1C electric current constant-current constant-voltage charging to 4.2V, cut-off electricity
0.05C is flowed, 10min is stood；Finally with 1C electric current constant-current charge to 6.3V, 1h is stood, observes battery core.If battery core is not exploded, no
It is on fire, then by experiment, conversely, then cannot.Obtained statistical result is as shown in table 2.
Table 2
From table 2 it can be seen that lithium ion battery 90% made from embodiment 6~8 can overcharge experiment, using without changing
Property foil be collector comparative example lithium ion battery 10% can overcharge experiment, it can be seen that afflux provided by the invention
Body can be improved the security performance of battery.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of composite current collector, which is characterized in that including collector and be formed in the surface covering of the collector, the table
Finishing coat includes nanometer bismuth, nano bismuth oxide, binder and conductive agent.
2. composite current collector as described in claim 1, which is characterized in that the nanometer bismuth, the nano bismuth oxide, described viscous
The mass ratio for tying agent and the conductive agent is (6~8): (0.5~1.5): (0.1~0.5): (0.1~0.5).
3. the preparation method of composite current collector as claimed in claim 1 or 2, which is characterized in that the partial size of the nanometer bismuth is
5nm~100nm；The partial size of the nano bismuth oxide is 10nm~100nm.
4. composite current collector as claimed in claim 1 or 2, which is characterized in that it is micro- that the thickness of the surface covering is no more than 2
Rice.
5. composite current collector as claimed in claim 1 or 2, which is characterized in that the binder is selected from butadiene-styrene rubber, acrylic acid
At least one of resin, carboxymethyl cellulose, ptfe emulsion, Kynoar and polyvinyl alcohol；
The conductive agent in carbon black, acetylene black, carbon fiber, carbon nanotube, graphene, Ketjen black, SP and KS-6 at least
It is a kind of.
6. composite current collector as claimed in claim 1 or 2, which is characterized in that the collector is selected from aluminium foil, nickel foam, nickel
Foil, nickel screen, copper mesh, copper foil, stainless (steel) wire, stainless steel Punching steel strip, stainless steel foil, titanium foil, titanium net, lead foil, lead cloth, graphitization
At least one of carbon cloth and graphene cloth material.
7. a kind of preparation method of composite current collector, which comprises the following steps:
Nanometer bismuth, nano bismuth oxide, binder and conductive agent are mixed in a solvent, obtain slurry；
The slurry is coated on to the surface of collector, drying obtains composite current collector.
8. a kind of electrode, which is characterized in that including the described in any item composite current collectors of claim 1~6 and be formed in described
Active material layer on the surface covering of composite current collector.
9. electrode as claimed in claim 8, which is characterized in that the electrode is lithium ion battery electrode；The electrode is
Anode, the active material layer contain tertiary cathode material；Or the electrode is cathode, it is negative that the active material layer contains graphite
Pole material.
10. a kind of lithium ion battery, which is characterized in that at least one of the anode of the lithium ion battery and cathode is as weighed
Benefit requires 8~9 described in any item electrodes.
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| EP3916862A4 (en) * | 2019-12-26 | 2022-06-29 | Zhuhai CosMX Battery Co., Ltd. | Current collector, preparation method therefor and application thereof |
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| CN109659565B (en) | 2023-04-07 |
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