CN104916811A - Non-diaphragm lithium ion battery and pole piece thereof - Google Patents
Non-diaphragm lithium ion battery and pole piece thereof Download PDFInfo
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- CN104916811A CN104916811A CN201510200896.2A CN201510200896A CN104916811A CN 104916811 A CN104916811 A CN 104916811A CN 201510200896 A CN201510200896 A CN 201510200896A CN 104916811 A CN104916811 A CN 104916811A
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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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- 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
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Abstract
The invention discloses a non-diaphragm lithium ion battery and a pole piece thereof, the pole piece includes a current collector, the front and / or the back side of the current collector is coated with a polar active material layer, the front and the back side of the current collector is also respectively coated with ceramic layers, and the polar active material layer is located between the ceramic layers and the current collector, and by use of the technical scheme, the volume energy density of the battery can be improved.
Description
Technical field
The present invention relates to field of lithium ion battery, particularly relate to a kind of aseptate lithium ion battery and pole piece thereof.
Background technology
The structure of current lithium ion battery mainly comprises positive plate, negative plate, is spaced apart between the positive plate and negative plate of arbitrary neighborhood by barrier film.Barrier film is as the important component part of current lithium ion battery, and barrier film is a kind of polymer-function material with nano micropore structure capable, its Main Function be battery plus-negative plate is separated, Electolyte-absorptive, only allow a lithium ion by, do not allow electronics to pass through.
The present inventor is carrying out finding in research process of the present invention, and the lithium ion battery of prior art exists following defect:
Due to the restriction of manufacturing process, barrier film is as the part less to battery capacity contribution, and it occupies the more volume of lithium ion battery, causes the volume energy density of lithium ion battery limited.
Summary of the invention
One of object of the embodiment of the present invention is to provide a kind of aseptate lithium ion battery and pole piece thereof.Apply the volume energy density that this technical scheme is conducive to improving battery.
A kind of lithium ion battery pole piece that the embodiment of the present invention provides, comprising:
Collector, has active material layer in the front of described collector and/or backside coating,
Also ceramic layer is coated with respectively in the front of described collector and the back side,
Described active material layer is between described ceramic layer and described collector.
Alternatively, on described collector, along the first side of the length direction of described collector, the second side is also coated with described ceramic layer respectively.
Alternatively, on described collector, be also coated with described ceramic layer respectively along the first end face of the Width of described collector, the second end face.
Alternatively, the thickness of each described ceramic layer is less than or equal to 10 μm.
Alternatively, the thickness of each described ceramic layer is 0.5 μm-5 μm.
Alternatively, be also coated with respectively at the end face of each described ceramic layer: polyolefin resin layer.
Alternatively, described polyolefin resin layer is: polyethylene layer or polypropylene layer.
Alternatively, the thickness of each described polyethylene layer or polypropylene layer is less than or equal to 10 μm.
Alternatively, the thickness of each described polyethylene layer or polypropylene layer is 0.5 μm-2 μm.
Alternatively, described pole piece is positive plate or negative plate.
The aseptate lithium ion battery of the one that the present embodiment provides, comprising:
Mutually face-to-face just to the first pole piece sticked together mutually and the second pole piece,
Described first pole piece is the arbitrary described pole piece of claim 1 to 10;
The second active material layer is had in the front of the collector of described second pole piece and/or backside coating,
Described first pole piece is the arbitrary of positive plate or negative plate, and described second pole piece is another of positive plate or negative plate.
Alternatively, described first pole piece is: negative plate, and described second pole piece is positive plate.
Alternatively, described battery is laminated lithium ion battery.
11, an aseptate lithium ion battery, is characterized in that, comprising:
Mutually face-to-face just to the first pole piece sticked together mutually and the second pole piece,
Described first pole piece is the arbitrary described pole piece of claim 1 to 10;
The second active material layer is had in the front of the collector of described second pole piece and/or backside coating,
Described first pole piece is the arbitrary of positive plate or negative plate, and described second pole piece is another of positive plate or negative plate.
12, aseptate lithium ion battery according to claim 11, is characterized in that,
Described first pole piece is: negative plate, and described second pole piece is positive plate.
13, the aseptate lithium ion battery according to claim 11 or 12, is characterized in that,
Described battery is laminated lithium ion battery.
Therefore, application the present embodiment technical scheme, the battery of pole piece structure is adopted in lithium ion battery, can directly make directly to be affixed between the positive plate of battery and negative plate and without the need to re-using barrier film, be conducive to the space of improving positive plate and negative plate in space, improve the volume energy density of battery.
Accompanying drawing explanation
Accompanying drawing described herein is used to provide a further understanding of the present invention, forms a application's part, does not form inappropriate limitation of the present invention.
A kind of structural representation of lithium ion battery pole piece of Fig. 1 for providing in the specific embodiment of the invention.
Reference numeral:
1: collector; 2: polar substances layer;
3: ceramic layer; 4: polyolefin resin layer.
Embodiment
Describe the present invention in detail below in conjunction with accompanying drawing and specific embodiment, be used for explaining the present invention in this illustrative examples of the present invention and explanation, but not as a limitation of the invention.
Shown in Figure 1, a kind of lithium ion battery pole piece provided herein is as signal, this pole piece comprises collector 1, in the front of collector 1, one of them face at the back side or be coated with active material layer 2 respectively on the two sides at front and the back side, also be coated with ceramic layer 3 respectively in the front of collector 1 and the back side, active material layer 2 is coated between ceramic layer 3 and collector 1.
For example: when this pole piece adopts one side coated structure formula, in the one side of collector 1, ceramic layer 3 is coated on collector 1, and at the another side of collector 1, ceramic layer 3 is coated on active material layer 2, covers this active material layer 2; When pole piece adopts dual coating structure, at front and the back side of collector 1, ceramic layer 3 is all coated on active material layer 2, covers on active material layer 2.
As the signal of the present embodiment, the collector 1 of this above-mentioned pole piece is also coated with ceramic layer 3 respectively along the both sides (being designated as the first side, the second side) of the length direction of collector 1, on the first side, the second side, this ceramic layer 3 is bonded on collector 1.Thus make from the cross section of the width end face of pole piece, ceramic layer 3 is wrapped in the surrounding of this cross section.
As the further signal of the present embodiment, two opposing end surfaces (being designated as the first end face, the second end face) that can also be positioned at the width end of collector 1 on the collector 1 of the pole piece of the present embodiment are coated with ceramic layer 3 further respectively, make so six of whole pole piece faces are coated with ceramic layer 3.
As the signal of the present embodiment, can also apply polyolefin resin layer 4 on each ceramic layer 3 of collector 1, this polyolefin resin film layer 4 can be, but not limited to the composite bed into polypropylene layer or polyethylene layer or polypropylene layer and the mutual layered structure of polyethylene layer are formed.
As the signal of the present embodiment, at the further coating polyethylene layer of ceramic layer 3 end face at the front of collector 1 and the back side; Or, can also but be not limited to further, in the first side, the end face coating polyethylene layer of the ceramic layer 3 of the second side; Or, can also but be not limited to further, at the end face coating polyethylene layer of the ceramic layer 3 of the first end face, the second end face.
As the signal of the present embodiment, above-mentioned pole piece can be the arbitrary of positive plate or negative plate.
When this pole piece is positive plate, the collector 1 of this positive plate can be, but not limited to select aluminium foil, and the active material on it is the positive active material containing lithium ion active material.
When this pole piece is negative plate, the collector 1 of this negative plate can be, but not limited to select Copper Foil, and the active material on it is positive electrode active materials, such as is generally carbon material.
Embodiment adopts arbitrary pole piece of said structure as one of positive plate or negative plate, can be made into the lithium ion battery without the need to diaphragm.
Therefore, the battery of above-mentioned pole piece structure is adopted in lithium ion battery, the positive plate of battery and negative plate can be directly made directly to be affixed and without the need to re-using barrier film, be conducive to the space of improving positive plate and negative plate in space, improve the volume energy density of battery, and simplify the lamination process of lithium ion battery, be conducive to improving process efficiency.
The thinnest membrane thicknesses is 12um at present in the prior art, and adopt the present embodiment technical scheme, the coating thickness of ceramic layer 3 is the thinnest can be several microns, be for example 0.5um, 0.8um, 1um, 2um, 3um, 4um, 5um, 7um etc., it is thinner that poly coating thickness can do, such as be 0.5um, 1um, 2um, 3um, 4um, 6um etc.Visible, relative to prior art, adopt the present embodiment technical scheme to breach the diaphragm thickness limit of prior art, the ceramic layer 3 of coating and the thickness summation of polyethylene layer can be less than ten microns, be conducive to the thickness greatly reducing battery core, improve the volume energy density of battery core.
In addition, the present embodiment adopts the ceramic layer 3 that is coated on pole piece and polyolefin resin layer 4 to substituted for diaphragm, plays outside the effect identical with diaphragm, adopts this structure also to have following beneficial effect further:
1, ceramic layer 3 possesses higher hydrophily, has better imbibition ability to electrolyte, can improve the distributing homogeneity of lithium battery inside battery electric current in charge and discharge process;
2, ceramic layer 3 intensity is high, and it is for the barrier film be easily punctured, and more can reduce the short circuit ratio of battery core, improves security performance;
3, adopt said structure to break through the thickness limit of current barrier film preparation technology, greatly reduce the thickness of battery core, improve the volume energy density of battery core.
4, in the present embodiment at the top of ceramic layer 3 further coating polyethylene layer, the aperture of this pole piece can be adjusted further by the coating density of polyolefin resin layer 4, be adjusted to the requirement meeting present battery, ensure the resistance that battery is low and high example conductivity, guarantee that lithium ion has good permeability, and polyethylene layer is combined with ceramic layer 3 and makes to have good strength character and flexility and tensile property, make up ceramic layer 3 intensity greatly but the defect easily cracked, improve the consistency of performance of battery.
5, in existing lithium ion battery, require that barrier film has following performance: when battery temperature raises near the cut-off current temperature reaching barrier film, the hole of barrier film caves in, form one deck atresia insulating barrier in-between the electrodes, the internal resistance of battery sharply increases, current channel in battery is cut off, thus stops the further generation of cell electrochemical reaction, avoids battery temperature too high and blasts.And the polyethylene layer at the present embodiment interval between positive electrode material layer negative electrode material layer has lower cut-off current temperature (being about about 130 DEG C), be applied on the pole piece of the present embodiment, be conducive to before battery explosion, cell electrochemical reaction being interrupted, to ensure the security performance of battery.
6, experiment proves, adopts ceramic layer 3 and the combination of polyethylene layer, can guarantee the fail safe of battery, can reduce again the short circuit ratio of battery.
7, in addition, the present embodiment at the two sides of pole piece and/or end face also coated ceramic layer 3 and polyolefin resin layer 4, can avoid active material layer 2 from the side or end face spill and contact with another pole piece and cause short circuit.The technical scheme adopting this surrounding comprehensively to wrap up can be implemented in the short circuit ratio not increasing the low battery of the cell thickness enterprising step-down in basis, improves the fail safe of battery.
Wherein, ceramic layer 3 material in the present embodiment is Al
2o
3.
reference examples:
This reference examples provides a kind of laminated lithium ion battery, and the specification of this battery is ASP7042126-S2A-3700mAh.Wherein, AS represents pure cobalt water-base cathode, and 7042126 represent that the thick, wide, long of this polymer Li-ion battery is of a size of 7mm, 42mm, 126mm, S represents that nominal multiplying power is 20C, 2 represent that battery is high capacity type, and A represents just very pure cobalt acid lithium, the nominal capacity of 3700 expression batteries
The positive plate of this battery, the collector front of negative plate and the back side are coated with active material layer, expose outside outside the active material layer of wherein each pole piece.
Positive plate in this battery and negative plate and diaphragm mutually stacked, positive plate is adopted to enter a bag technique, namely positive plate loads with in diaphragm bag, the two-layer of diaphragm bag mutually sews up connection by interval electric welding on two length edges, the diaphragm bag of positive plate is housed and negative pole is mutually stacked makes laminated lithium ion battery, then carry out encapsulating, the heat-sealing of electrolyte filling, secondary, change into, the conventional batteries preparation technology such as partial volume make.
Ceramic diaphragm sheet in this reference examples is made up of ceramic layer and polyethylene layer, the width of this ceramic diaphragm sheet and length are greater than negative plate and positive plate slightly, positive plate and negative plate separate by barrier film, and the thickness of the ceramic diaphragm that the present embodiment adopts is almost the thinnest at present 12 μm.
embodiment 1:
The same reference examples of specification of the laminated lithium ion battery of the present embodiment.
The positive plate of the present embodiment battery comprises collector, has active material layer and ceramic layer in collector front surface coated, has ceramic layer at the backside coating of collector.Wherein the thickness of each layer ceramic layer is 2 μm.
The collector of the negative plate of the present embodiment is coated with active material layer, and active material layer exposes outside and uncoatedly has ceramic layer or polyethylene layer.
Adopt the positive plate of the present embodiment and negative plate mutually stacked, make any two adjacent positive plates, negative plate just stick together stacked face-to-face mutually, obtain a laminated lithium ion battery.
The length of the collector of above-mentioned positive plate and width be dimensioned slightly smaller than negative plate.After the side of positive plate is coated with ceramic layer, positive plate be slightly narrower than negative plate or with negative plate with wide, and width broadens due to the coating of ceramic layer can't to cause the width of laminated batteries, be conducive to the Miniaturization Design of battery, improve the volume energy density of battery.
embodiment 2:
The difference of the present embodiment and embodiment 1 is only:
The surface of the ceramic layer at the present embodiment collector front and the back side is also coated with polyethylene layer, and the thickness of polyethylene layer is 1 μm.
embodiment 3:
The battery of the present embodiment and the difference of embodiment 2 are only:
First side of the present embodiment collector and the second side are also bonded with ceramic layer, and the thickness of the ceramic layer at this place is 2 μm.
embodiment 4:
The difference of the present embodiment battery and embodiment 3 is only:
Also be bonded with polyethylene layer in the first side of the present embodiment collector and the top face of ceramic layer of the second side, the poly thickness at this place is 1 μm.
embodiment 5:
The difference of the present embodiment battery and embodiment 4 is only:
Also be bonded with ceramic layer at the first end face of the present embodiment collector, the second end face end face, the thickness of the ceramic layer at this place is 2 μm.
embodiment 6:
The difference of the present embodiment battery and embodiment 5 is only:
Also be bonded with polyethylene layer in the first end face of the present embodiment collector, the top face of ceramic layer of the second end face, the thickness of the polyethylene layer at this place is 1 μm.
embodiment 7:
The difference of the present embodiment battery and embodiment 6 is only:
Active material layer on the collector of the present embodiment positive plate exposes outside, and uncoated in the periphery of positive plate have ceramic layer or polyethylene layer or other coatings;
Active material layer on the collector of the present embodiment negative plate, in the front of negative plate, the back side and the first side, the second side and the first width end face, the second width end face be coated with ceramic layer and polyethylene layer in turn, ceramic layer cover by polyethylene layer, polar material cover by ceramic layer, ceramic layer thickness is everywhere 2 μm, and the thickness of polyethylene layer is 1 μm.
embodiment 8:
The difference of the present embodiment battery and embodiment 6 is only:
The ceramic layer external coating of the front of the present embodiment positive plate, the back side, the first side, the second side, the first end face, the second end face is: polypropylene layer, but not polyethylene layer, the thickness of the polypropylene layer at this place is 1 μm.
embodiment 9:
The difference of the present embodiment battery and embodiment 6 is only:
On the front of the positive plate of the present embodiment, the back side, the first side, the second side, the first end face, the second end face, coating order is different, specifically, polyethylene layer is positioned at internal layer, and ceramic layer is positioned at skin, the thickness of the polyethylene layer at this place is 1 μm, and ceramic layer thickness is 2 μm.
Experimental analysis:
The chance sample 100 of the laminated lithium ion battery of obtained above-mentioned reference examples, embodiment 1-9 structure respectively, carries out short circuit and volume energy density and thermal shock resistance properties to grab sample and tests.
Wherein thermal shock resistance test is, the battery standing completely filled by battery is in hot case, then the thermocouple operational heat being fixed on the large centre of surface position of battery is made, rise to (130 ± 2) DEG C with the temperature rise rate of (5 ± 2) DEG C/min, and be incubated 60min, observe its blast whether on fire, can normally work if battery does not damage, then think by heat shock resistance test (being designated as Pass), otherwise do not pass through.
To each group of test result calculating mean value respectively, obtain the experimental data mean value table of comparisons shown in table one:
Table one: the experimental data mean value table of comparisons
| Project | Short circuit ratio | Volume energy density | Heat shock resistance (130 DEG C, 60min) |
| Reference examples | 0.11％ | 457.2Wh/L | 55％pass |
| Embodiment 1 | 5.77％ | 525.6Wh/L | 36％pass |
| Embodiment 2 | 3.12％ | 522.5Wh/L | 92％pass |
| Embodiment 3 | 1.70％ | 522.5Wh/L | 93％pass |
| Embodiment 4 | 1.66％ | 522.5Wh/L | 95％pass |
| Embodiment 5 | 0.15％ | 522.5Wh/L | 95％pass |
| Embodiment 6 | 0.03％ | 522.5Wh/L | 100％pass |
| Embodiment 7 | 0.03％ | 521.9Wh/L | 100％pass |
| Reference examples 8 | 0.03％ | 522.5Wh/L | 74％pass |
| Reference examples 9 | 0.07％ | 522.5Wh/L | 92％pass |
Visible according to table one, relative to the technical scheme of the employing positive plate bag of prior art, pole piece wraps up ceramic layer and polyolefin resin layer (polyethylene layer or polypropylene layer) respectively, the volume energy density of battery can be improved, greatly can reduce again the circuit rate of battery and improve the thermal shock resistance of battery; Relative to the technical scheme of the ceramic layer skin coating polypropylene material at pole piece, adopt the technical scheme at the outer coating polyethylene material of ceramic layer, greatly can improve the thermal shock resistance of battery, battery can be made again when temperature reaches certain high temperature from turning off, avoid battery to cross thermal explosion, be conducive to the fail safe improving battery.
In addition, the present inventor is carrying out finding in research process of the present invention, relative to first applying polyolefin resin layer coated ceramic layer technical scheme (being scheme one) again, what adopt the present embodiment to recommend first applies the technical scheme (being scheme two) that polyolefin resin film layer is coated with ceramic layer again, is conducive to the short circuit ratio and the raising thermal shock resistance that greatly reduce battery.
In addition, pole piece all can with certain pole powder, pole powder likely punctures barrier film, employing scheme one, pole acne can through the crackle of ceramic layer and cathode contact after breaking polyolefin resin film layer, easily cause battery core short circuit, and may become large at the crackle of battery ceramic layer in heat-shock process, the thermal shock resistance of battery can be made to be deteriorated, and during the scheme two of employing, outer field vistanex can make the crackle of ceramic layer up, compared to scheme two, can be relatively thick at the polyolefin resin layer of the cracks of ceramic layer, thus make up the crackle of ceramic layer, guarantee that the short circuit ratio of the lithium ion battery of scheme two structure is lower, thermal shock resistance is better.
In addition, the present inventor is carrying out finding in research process of the present invention, coated ceramic layer on pole piece, and the ceramic material of Nano grade granularity has the resistance to elevated temperatures of high-quality, even if at high temperature it still keeps good mechanical structure; Nano grade granularity in addition in this ceramic layer forms solid solution in pole piece, has good imbibition ability and liquid-keeping property, is conducive to greatly improving the doubly forthright of battery and cyclicity; And the hydrofluoric acid (HF) dissociated during high ceramic layer is all right and in electrolyte, improves the acid resistance of battery, thus improves the fail safe of battery.
In addition, the present inventor is carrying out finding in research process of the present invention, pole piece structure outside pottery is wrapped in relative to selecting polypropylene, select the polyethylene pole piece structure be wrapped in outside ceramic layer can improve the heat resistance of battery further, make when battery temperature reaches predetermined temperature upper limit, battery can realize, from turning off, stopping electrochemical reaction, avoids battery high-temperature to explode and avoids the generation of accident.
And, can prevent moisture from entering pole piece at pole piece periphery coated ceramic layer and polyethylene layer (or combination of polypropylene layer or two groups), reduce the baking time of pole piece and battery core, shorten the production cycle of battery, and the tensile property of this polyethylene layer (or combination of polypropylene layer or two groups) firmly can wrap up pole piece in the use procedure of battery, motor material is avoided to be scattered, be specially adapted to bent flexible lithium ion battery, when being applied on this flexible lithium ion battery, battery can bend by user in the larger context, distortion, the arrival of dressing product for electronics brings wide prospect.
Above-described execution mode, does not form the restriction to this technical scheme protection range.The amendment done within any spirit at above-mentioned execution mode and principle, equivalently to replace and improvement etc., within the protection range that all should be included in this technical scheme.
Claims (10)
1. a lithium ion battery pole piece, is characterized in that, comprising:
Collector, has active material layer in the front of described collector and/or backside coating,
Also ceramic layer is coated with respectively in the front of described collector and the back side,
Described active material layer is between described ceramic layer and described collector.
2. lithium ion battery positive plate according to claim 1, is characterized in that,
On described collector, along the first side of the length direction of described collector, the second side is also coated with described ceramic layer respectively.
3. lithium ion battery positive plate according to claim 1, is characterized in that,
On described collector, be also coated with described ceramic layer respectively along the first end face of the Width of described collector, the second end face.
4. lithium ion battery positive plate according to claim 1, is characterized in that,
The thickness of each described ceramic layer is less than or equal to 10 μm.
5. lithium ion battery positive plate according to claim 4, is characterized in that,
The thickness of each described ceramic layer is 0.5 μm-5 μm.
6., according to arbitrary described lithium ion battery pole piece of claim 1 to 5, it is characterized in that,
Also be coated with respectively at the end face of each described ceramic layer: polyolefin resin layer.
7. lithium ion battery pole piece according to claim 6, is characterized in that,
Described polyolefin resin layer is: polyethylene layer or polypropylene layer.
8. lithium ion battery pole piece according to claim 7, is characterized in that,
The thickness of each described polyethylene layer or polypropylene layer is less than or equal to 10 μm.
9. lithium ion battery pole piece according to claim 8, is characterized in that,
The thickness of each described polyethylene layer or polypropylene layer is 0.5 μm-2 μm.
10., according to arbitrary described lithium ion battery pole piece of claim 1 to 5, it is characterized in that,
Described pole piece is positive plate or negative plate.
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