CN105591068A - A manufacturing method of a cathode plate used for a lithium ion battery with high specific energy - Google Patents
A manufacturing method of a cathode plate used for a lithium ion battery with high specific energy Download PDFInfo
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- CN105591068A CN105591068A CN201410571173.9A CN201410571173A CN105591068A CN 105591068 A CN105591068 A CN 105591068A CN 201410571173 A CN201410571173 A CN 201410571173A CN 105591068 A CN105591068 A CN 105591068A
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- positive plate
- lithium ion
- ion battery
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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 relates to a manufacturing method of a cathode plate used for a lithium ion battery with high specific energy. The cathode plate includes a high-nickel ternary material cathode plate. The method is characterized in that the method includes 1) preparing oxide slurry, and 2) coating both surfaces of the high-nickel ternary material cathode plate with the oxide slurry, and drying to form oxide coatings on the two surfaces of the high-nickel ternary material cathode plate, with the thickness of the coatings being 10 [mu]m or below, thus finishing a manufacturing process of the cathode plate used for the lithium ion battery with high specific energy. The surfaces of an electrode adopting a high-nickel ternary material as a cathode active compound are coated with the oxide coatings, and therefore a barrier function for reducing the reaction active area between surfaces of the high-nickel ternary material electrodes and an electrolyte is achieved, side reactions in a battery are effectively inhibited, stability during high-temperature storage and long-term cycling of batteries adopting the high-nickel ternary material as a cathode is ensured, storage and cycle service lifetimes of the batteries are greatly prolonged, and safety of the batteries is ensured because diffusion of micro short circuit points in the batteries is inhibited.
Description
Technical field
The invention belongs to technical field of lithium ion, particularly relate to a kind of energy-density lithium ion batteryBy the preparation method of positive plate.
Background technology
Lithium ion battery, as the advanced battery that a kind of phase early 1990s grows up, has heightThe series of advantages such as specific energy, high voltage, wide operating temperature range, low self-discharge rate and memory-less effect,There is in recent years application widely in fields such as Aero-Space, space power system field, especially electric motor cars.Along with the continuous expansion of application, particularly also more and more higher to the requirement of lithium ion battery specific energy, andThe specific energy of lithium ion battery and the material system of positive and negative plate are closely related.
At present, in the material system of the lithium ion battery positive and negative plate being widely used, positive electrode masterWill be with traditional cobalt acid lithium (LiCoO2), LiMn2O4 (LiMn2O4), LiFePO4 (LiFePO4)、Nickel cobalt manganese (1:1:1) and nickel cobalt lithium system are main, and the main and graphite-like of negative material is main, these electrodesThe advantage of material is that technique for applying is relatively ripe, and long-term cycle performance is relatively stable, deficiencyBe in the restriction that is subject to material system, cause the specific capacity of electrode material to be difficult to improve, above-mentioned positive electrodeTheoretical specific capacity is all below 200mAh/g, and according to lithium ion battery development trend from now on, above-mentioned positive poleThe specific capacity of material far from meets the instructions for use of battery. For energy-density lithium ion battery characteristicDemand, has developed nickelic ternary material positive electrode system, its specific capacity can reach 200mAh/g withUpper, but due to the distinctive nickelic composition of nickelic ternary material, the cycle performance under its high voltage is poor. For carryingCycle performance under high high voltage, applies one deck lithium cobaltate cathode slurry also at nickelic ternary material electrode surfacePositive plate is made in oven dry, and the energy-density lithium ion battery that adopts this positive plate to make, has reduced gas production,Alleviate ballooning, improved battery, but due to the having relatively high expectations of electrode coating processes,Technological feasibility is lower, and battery specific energy is subject to the restriction of cobalt acid lithium system, has reduced nickelic ternary material originallyThe battery specific energy of material electrode, and there is security hidden trouble in battery.
Summary of the invention
The present invention solves the technical problem existing in background technology, provides battery to have high-energy-density, heightThe preparation method of positive plate for the energy-density lithium ion battery of security feature.
The present invention includes following technical scheme:
The preparation method of positive plate for energy-density lithium ion battery, comprises nickelic ternary material positive plate,Be characterized in: comprise the following steps:
Step 1 is that 100nm and following oxide powder and binding agent, solvent stir into by particle diameterSolid content is 2%～30% oxide slurry;
The oxide slurry that step 2 is made step 1 is coated in described nickelic ternary material positive plate twoFace, more than drying 10min at 100 DEG C～120 DEG C temperature, the nickelic ternary material positive plate two sides after oven dryAll forming thickness is 10 μ m and following oxide coating, completes high-energy-density lithium-ion electric of the present inventionThe manufacturing process of positive plate for pond.
The present invention can also adopt following technical measures:
The oxide slurry of in step 2, step 1 being made is coated in described nickelic ternary material positive plate twoThe method of face is for to complete by spraying equipment, and the thickness of positive plate two sides oxide coating passes through spraying equipmentDie head parameter control.
The oxide slurry of in step 2, step 1 being made is coated in described nickelic ternary material positive plate twoThe method of face is for to complete by gravure printing apparatus, and the thickness of positive plate two sides oxide coating passes through intaglio plateSize and the density of printing equipment pit are controlled.
Described oxide is the one of aluminium oxide, magnesia, zirconia or fluoride.
Described binding agent is water system binding agent or organic system binding agent.
Described binding agent is the one of carboxymethyl cellulose class, butadiene-styrene rubber or Kynoar.
Described solvent is organic solvent.
Described solvent is the one of water, N methyl pyrrolidone or acetone.
Advantage and good effect that the present invention has are:
The present invention applies one deck oxide by the electrode surface that is positive active material at nickelic ternary materialCoating, has played barrier work to the reactivity area that reduces nickelic ternary material electrode surface and electrolyteWith, effectively suppress the generation of inside battery side reaction, ensure that nickelic ternary material is anodal batteryIn the stability of high-temperature storage and long-term circulation time, greatly improve storage and the cycle life of battery,And owing to having suppressed the diffusion of inside battery micro-short circuit point, ensure the security of battery.
Brief description of the drawings
Fig. 1 is the energy-density lithium ion battery positive plate structural representation of making in the present invention;
Fig. 2 is the battery and current known batteries loop-around data curve comparison figure that the present invention makes.
In figure: 1-collector, 2-oxide coating, the nickelic ternary material coating of 3-.
Detailed description of the invention
For further disclosing summary of the invention of the present invention, Characteristic, detailed especially exemplified by following instanceBe described as follows:
The preparation method of positive plate for energy-density lithium ion battery, comprises nickelic ternary material positive plate,Be characterized in: comprise the following steps:
Step 1 is that 100nm and following oxide powder and binding agent, solvent stir into by particle diameterSolid content is 2%～30% oxide slurry;
The oxide slurry that step 2 is made step 1 is coated in described nickelic ternary material positive plate twoFace, more than drying 10min at 100 DEG C～120 DEG C temperature, the nickelic ternary material positive plate two sides after oven dryAll forming thickness is 10 μ m and following oxide coating, completes high-energy-density lithium-ion electric of the present inventionThe manufacturing process of positive plate for pond.
Wherein, the oxide slurry of in step 2, step 1 being made is just being coated in described nickelic ternary materialThe method on pole piece two sides is for to complete by spraying equipment, and the thickness of positive plate two sides oxide coating is by sprayThe die head parameter of automatic doubler surface glouer is controlled; Or the oxide slurry of in step 2, step 1 being made appliesIn the method on described nickelic ternary material positive plate two sides for to complete by gravure printing apparatus, positive plate twoThe thickness of face oxide coating is controlled by size and the density of gravure printing apparatus pit.
Described oxide is the one of aluminium oxide, magnesia, zirconia or fluoride.
Described binding agent is water system binding agent or organic system binding agent.
Described binding agent is the one of carboxymethyl cellulose class, butadiene-styrene rubber or Kynoar.
Described solvent is organic solvent.
Described solvent is the one of water, N methyl pyrrolidone or acetone.
Comparative example 1
Step 1, to adopt nickelic ternary material be positive active material, adds carbon black (SP) as conductionAgent, Kynoar (PVDF) are that binding agent, nitrogen methyl pyrrolidone (NMP) are solvent, adoptAbove-mentioned material is mixed with to nickelic ternary material slurry with refiner, wherein each material mass proportioning is: heightNickel ternary material: conductive agent: binding agent: solvent=95:3:2:55;
Step 2, the nickelic ternary material slurry that step 1 is made are coated in 20 μ as collector 1The two sides of m aluminium foil, after oven dry, forms nickelic ternary material for current known energy-density lithium ion batteryMaterial positive plate 3.
Embodiment 1
Step 1, taking carboxymethyl cellulose class (CMC) and butadiene-styrene rubber (SBR) as binding agent, taking water asSolvent, with the alumina powder mix and blend of D50 particle diameter at 500nm; Wherein, aluminium oxide: CMC:SBR:The mass ratio of water is 100:1.2:1.2:250, forms oxide slurry;
Step 2, the oxide slurry of using the spraying equipment that carries baking oven that step 1 is made are evenly coated inThe nickelic ternary material positive plate two sides that comparative example 1 is made, bake out temperature is 110 DEG C, drying time is10min, nickelic ternary material positive plate two sides all forms oxide coating 2, by the die head of spraying equipmentThe thickness of parameter control positive plate two sides oxide coating, measures nickelic ternary material positive plate with calibratorTwo sides oxide coating thickness is below 5 μ m, completes high-energy-density lithium ion of the present invention shown in Fig. 1The manufacturing process of positive electrode for battery sheet.
Embodiment 2
The manufacturing process phase of oxide slurry in the manufacturing process of step 1, oxide slurry and embodiment 1With;
Step 2, the oxide slurry of using the spraying equipment that carries baking oven that step 1 is made are evenly coated inThe nickelic ternary material positive plate two sides that comparative example 1 is made, bake out temperature is 110 DEG C, drying time is10min, nickelic ternary material positive plate two sides all forms oxide coating 2, by the die head of spraying equipmentThe thickness of parameter control positive plate two sides oxide coating, measures nickelic ternary material positive plate with calibratorTwo sides oxide coating thickness is that 5 μ m are above to 10 μ m, completes high specific energy of the present invention shown in Fig. 1The manufacturing process of positive plate for amount lithium ion battery.
Embodiment 3
Step 1, taking carboxymethyl cellulose class (CMC) and butadiene-styrene rubber (SBR) as binding agent, taking water asSolvent, with the alumina powder mix and blend of D50 particle diameter at 800nm; Wherein, aluminium oxide: CMC:SBR:The mass ratio of water is 100:1.2:1.2:250, forms oxide slurry;
Step 2, the oxide slurry of using the gravure printing apparatus that carries baking oven that step 1 is made are evenly coated withOverlay on the nickelic ternary material positive plate two sides that comparative example 1 is made, bake out temperature is 110 DEG C, when oven dryBetween be 15min, nickelic ternary material positive plate two sides all forms oxide coating 2, establishes by intaglio printingThe standby size of pit and the thickness of density control positive plate two sides oxide coating, nickelic with calibrator measurementTernary material positive plate two sides oxide coating thickness is≤5 μ m, completes the high ratio of the present invention shown in Fig. 1The manufacturing process of positive plate for energy lithium ion battery.
Adopt respectively high-energy-density lithium that embodiment 1, embodiment 2, embodiment 3 and comparative example 1 make fromSub-positive electrode for battery sheet, negative plate, barrier film and the electrolyte of employing same material, produce respectively 4 kinds18650 model lithium ion batteries. According to following battery testing method to 4 kind of 18650 model lithium-ion electricPerformance Evaluation is carried out respectively in pond:
Overcharge test: battery is with 0.2C constant-current constant-voltage charging to 4.2V, and 0.5A ends; After with 0.5C perseveranceCurrent charge stops to 5V, draws battery safety test result in table 1;
Short-circuit test: battery is with 0.2C constant-current constant-voltage charging to 4.2V, and 0.5A ends; By this full electric stateBattery carries out short circuit, and short-circuit resistance is 3m Ω, until cell voltage is reduced to 0V or battery temperature is nowFall rear 1h and stop, drawing battery safety test result in table 1;
Loop test: battery with 0.2C constant-current constant-voltage charging to 4.2V; Shelve 10min; Put with 0.5CElectricity is to 2.75V; Shelve 10min, carry out charge and discharge cycles, show that the present invention as shown in Figure 2 makesBattery and current known batteries loop-around data curve comparison figure.
Table 1 battery safety test result contrast table
| Overcharge test | Short-circuit test | |
| Embodiment 1 | ○ | ○ |
| Embodiment 2 | ○ | ○ |
| Embodiment 3 | ○ | ○ |
| Comparative example 1 | × | Zero (leakage) |
Remarks: in table 1: "○" representative: do not fire not quick-friedly, battery is by test; "×" represents electricityPond is on fire, and battery is not by test.
Can find out the high-energy-density lithium of selecting positive plate that the present invention makes to make by Fig. 2 and table 1Compared with the energy-density lithium ion battery that ion battery is made with current known positive plate, the present invention just makesThe energy-density lithium ion battery that pole piece is made, in possessing high-energy-density, has effectively improved batteryCycle performance and security performance.
Although above the preferred embodiments of the present invention are described, the present invention is not limited toThe detailed description of the invention of stating, above-mentioned detailed description of the invention is only schematically, is not restrictive,Those of ordinary skill in the art, under enlightenment of the present invention, is not departing from aim of the present invention and claimIn the scope situation of protecting, can also make a lot of forms. These all belong to protection scope of the present inventionWithin.
Claims (8)
1. the preparation method of positive plate for energy-density lithium ion battery, comprises nickelic ternary material positive poleSheet, is characterized in that: comprise the following steps:
Step 1 is that 100nm and following oxide powder and binding agent, solvent stir by particle diameterBecome the oxide slurry that solid content is 2%～30%;
The oxide slurry that step 2 is made step 1 is coated in described nickelic ternary material positive plate twoFace, more than drying 10min at 100 DEG C～120 DEG C temperature, the nickelic ternary material positive plate two after oven dryIt is 10 μ m and following oxide coating that face all forms thickness, completes high-energy-density lithium ion of the present inventionThe manufacturing process of positive electrode for battery sheet.
2. the preparation method of positive plate for energy-density lithium ion battery according to claim 1, its spyLevy and be: the oxide slurry of in step 2, step 1 being made is coated in described nickelic ternary material positive poleThe method on sheet two sides is for to complete by spraying equipment, and the thickness of positive plate two sides oxide coating is by sprayingThe die head parameter of equipment is controlled.
3. the preparation method of positive plate for energy-density lithium ion battery according to claim 1, its spyLevy and be: the oxide slurry of in step 2, step 1 being made is coated in described nickelic ternary material positive poleThe method on sheet two sides is for to complete by gravure printing apparatus, and the thickness of positive plate two sides oxide coating passes throughSize and the density of gravure printing apparatus pit are controlled.
4. the preparation method of positive plate for energy-density lithium ion battery according to claim 1, its spyLevy and be: described oxide is the one of aluminium oxide, magnesia, zirconia or fluoride.
5. the preparation method of positive plate for energy-density lithium ion battery according to claim 1, its spyLevy and be: described binding agent is water system binding agent or organic system binding agent.
6. the preparation method with positive plate according to energy-density lithium ion battery described in claim 1 or 5,It is characterized in that: described binding agent is the one of carboxymethyl cellulose class, butadiene-styrene rubber or Kynoar.
7. the preparation method of positive plate for energy-density lithium ion battery according to claim 1, its spyLevy and be: described solvent is organic solvent.
8. the preparation method with positive plate according to energy-density lithium ion battery described in claim 1 or 7,It is characterized in that: described solvent is the one of water, N methyl pyrrolidone or acetone.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105355854A (en) * | 2015-10-13 | 2016-02-24 | 中国电子科技集团公司第十八研究所 | Fabrication method of positive plate for high-energy-density lithium-ion battery |
| CN109817982A (en) * | 2018-12-27 | 2019-05-28 | 中国电力科学研究院有限公司 | A kind of lithium ion cell positive plate and its modified technique reducing Li dendrite security risk |
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| CN103560250A (en) * | 2013-11-07 | 2014-02-05 | 天津市捷威动力工业有限公司 | Lithium ion battery adopting lithium-rich manganese-based material as positive electrode and preparation method of lithium ion battery |
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Patent Citations (4)
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| CN101326661A (en) * | 2006-07-06 | 2008-12-17 | 松下电器产业株式会社 | Method and apparatus for manufacturing member for secondary battery and secondary battery using the same |
| CN103887471A (en) * | 2008-06-11 | 2014-06-25 | 索尼株式会社 | Electrode With Porous Protective Film, Nonaqueous Electrolyte Secondary Battery, And Method For Manufacturing Electrode With Porous Protective Film |
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| CN103560250A (en) * | 2013-11-07 | 2014-02-05 | 天津市捷威动力工业有限公司 | Lithium ion battery adopting lithium-rich manganese-based material as positive electrode and preparation method of lithium ion battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105355854A (en) * | 2015-10-13 | 2016-02-24 | 中国电子科技集团公司第十八研究所 | Fabrication method of positive plate for high-energy-density lithium-ion battery |
| CN109817982A (en) * | 2018-12-27 | 2019-05-28 | 中国电力科学研究院有限公司 | A kind of lithium ion cell positive plate and its modified technique reducing Li dendrite security risk |
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Application publication date: 20160518 |
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