CN102088086B - Method for preparing high-voltage lithium ion battery anode - Google Patents

Method for preparing high-voltage lithium ion battery anode Download PDF

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CN102088086B
CN102088086B CN2010106136115A CN201010613611A CN102088086B CN 102088086 B CN102088086 B CN 102088086B CN 2010106136115 A CN2010106136115 A CN 2010106136115A CN 201010613611 A CN201010613611 A CN 201010613611A CN 102088086 B CN102088086 B CN 102088086B
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lithium ion
ion battery
active material
binding agent
electrode active
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CN102088086A (en
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翟丽娟
朱广燕
刘志远
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Chery Automobile Co Ltd
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SAIC Chery Automobile Co Ltd
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Abstract

The invention relates to a high-voltage lithium ion battery anode, a lithium ion battery using the same and a preparation method of the high-voltage lithium ion battery anode. The high-voltage lithium ion battery anode comprises a current collector, an anode active substance material, a conduction agent and a binder, wherein 85-95wt% of anode active substance material, 2.5-7.5wt% of conduction agent and 2.5-7.5wt% of binder are prepared into a sizing agent; and the sizing agent is coated on the current collector. The lithium ion battery anode in the invention and the lithium ion battery using the anode have the advantages of high discharging voltage platform, high specific energy and low cost and are easy for large-scale industrial production.

Description

A kind of high-voltage lithium ion batteries anode preparation method
Technical field
The present invention relates to the lithium-ion battery energy technical field, it is anodal and use lithium ion battery and the preparation method of this positive pole particularly to relate to a kind of high-voltage lithium ion batteries.
Background technology
Lithium ion battery with regard to being subject to liking of users owing to its high voltage and high-energy-density, also has been subject to numerous researchers' attention since coming out.Particularly enter 21st century, fast development and the extensive use of various portable electric appts, radio mobile communication equipment, motor vehicle are for more height ratio capacity, service life cycle are grown, the demand of lithium ion battery seems more urgent cheaply.
The key that improves lithium ion battery high-energy-density index is the exploitation of high-energy-density positive electrode and the design of anode electrode, and most researchers has been put into the exploitation of the positive electrode of high-energy-density to main energy, and has ignored the design of anode electrode.
At present, dropped into the lithium ion battery of commercialization large-scale application, its anodal active material that adopts is LiCoO mostly 2, LiMn 2O 4, LiFePO 4, Li (Ni 1/3Co 1/3Mn 1/3) O 2, Li (Ni 1/3Co 1/3Al 1/3) O 2The actual specific capacity of these positive electrodes can reach 120-150mAh/g, and to carbon class negative discharge voltage platform mostly in 3.6V-3.8V (except the discharge voltage plateau of LiFePO4 is the 3.2V), the lithium ion battery that forms with the silicon-based anode alloy collocation of the carbon class negative pole of height ratio capacity and superelevation specific capacity, the raising of its specific energy is still limited, has therefore limited to a great extent the further raising of the specific energy of lithium ion battery.
Summary of the invention
In order to solve the low and low problem of discharge voltage plateau of existing lithium ion battery and anodal specific energy thereof, the lithium ion battery that the object of the invention is to provide a kind of high-voltage lithium ion batteries positive pole and uses this positive pole.
Adopt 5V high voltage binary material LiNi by positive active material xMn 2-xO 4Carry out composite modifiedly with carbon class material, with advanced person's technical recipe, electrode design and the manufacture craft thereof of optimization, produce the high-voltage lithium ion batteries positive pole.Adopt this positive pole, the negative pole of arranging in pairs or groups again, barrier film, electrolyte and battery case produce the lithium ion battery of high-voltage high-energy-density.
Concrete technical scheme is as follows:
A kind of high-voltage lithium ion batteries is anodal, comprise collector, the positive electrode active material material, conductive agent and binding agent, described positive electrode active material material, conductive agent and binding agent are according to the positive active material of weight proportion 85%-95%, and the conductive agent of 2.5%-7.5% and the binding agent of 2.5%-7.5% consist of slurry, and described slurry is coated on the described collector.
Further, the positive electrode active material material is 5V high voltage binary composite L iNi xMn 2-xO 4/ C, wherein, 0<x≤0.5.
Further, the positive electrode active material material is 5V high voltage binary composite L iNi 0.5Mn 1.5O 4/ C or LiNi 0.4Mn 1.6O 4/ C.
Further, described collector is aluminium foil, thickness 15 μ m-40 μ m, and the coated side density of described positive pole is 26mg/cm 2-35mg/cm 2
Further, described binding agent is one or both the mixture in Kynoar, the polytetrafluoroethylene, described conductive agent is the hybrid conductive agent, formed by super conductive black and super electrically conductive graphite, proportioning is 1: 1 (w: w), wherein, the weight proportion of conductive agent and binding agent use amount is (1.0-1.25): 1.
Use the lithium ion battery of above-mentioned high-voltage lithium ion batteries positive pole, comprise that each described high-voltage lithium ion batteries is anodal among the claim 1-5, negative pole is inserted in the barrier film between positive pole and the negative pole, electrolyte and battery case.
Further, described barrier film is polyethylene, polypropylene or polyethylene and polypropylene composite film, and described negative pole comprises negative electrode active material, conductive agent, binding agent and collector.
Further, this negative electrode active material is one or more in native graphite, Delanium, carbonaceous mesophase spherules, hard carbon, ashbury metal, silicon alloy, Si-C composite material, 3 SiC 2/graphite composite material and the lithium titanate material, this binding agent is one or both the mixture among Kynoar PVDF, polytetrafluoroethylene PTFE, styrene butadiene rubber sbr, the sodium carboxymethylcellulose CMC, this conductive agent is one or more the mixture in acetylene black, super conductive black, super electrically conductive graphite, the conductive carbon nanotube, and this collector is Copper Foil or aluminium foil.
The preparation method of above-mentioned high-voltage lithium ion batteries positive pole, further, adopt following steps:
(1) binding agent is dispersed in the middle of the solvent;
(2) with positive electrode active material material and conductive agent composition mixture, add in the container that passes into nitrogen or argon gas inert atmosphere;
(3) to the mixture ball milling, fully to be ground and evenly mix after join in the middle of the solvent, mix and obtain slurry;
(4) slurry is coated in above the collector aluminium foil, drying rolls, and cuts, and can obtain above-mentioned positive pole.
The preparation method of above-mentioned lithium ion battery, further, adopt following steps:
(1) binding agent is dispersed in the middle of the solvent;
(2) join in the middle of the solvent after negative electrode active material material and conductive agent are evenly mixed, mix, be coated in above the collector;
(3) drying rolls, and cuts, and obtains negative pole;
(4) positive pole, negative pole, the barrier film that is inserted between positive pole and the negative pole are assembled;
(5) by fluid confluence lug and connecting terminals are connected together, in the battery case of packing into;
(6) inject electrolyte, sealing changes into reprocessing.
Compare with present prior art, the lithium ion cell positive that the present invention prepares and use the lithium ion battery of this positive pole to have the discharge voltage plateau height, specific energy is high, and cost is low, is easy to large-scale industrial production.
Description of drawings
Fig. 1: be the charging and discharging curve figure of the invention process example 4 monomer lithium ion battery batteries.
Fig. 2: be the cyclic curve figure of the invention process example 4 monomer lithium ion battery batteries.
Embodiment
The below describes the present invention with reference to the accompanying drawings, and it is a kind of preferred embodiment in the numerous embodiments of the present invention.
High voltage 5V LiNi 0.5Mn 1.5O 4And LiNi 0.4Mn 1.6O 4Material all has lithium discharge platform voltage high (about 4.7V), actual specific capacity can reach 120-140mAh/g and cycle performance is good.LiNi wherein 0.4Mn 1.6O 4Material has two discharge voltage plateaus, is respectively 4.7V and 4.0V, and 5V LiNi 0.5Mn 1.5O 4The material discharging voltage platform mainly concentrates on the 4.7V district, with LiNi 0.4Mn 1.6O 4Compare, have the 4.7V discharge platform and increase, and reversible capacity is larger, the better characteristics of cyclical stability.If materials through composite modified, is used for lithium ion cell positive with advanced person's technical recipe and electrode design, will greatly improves voltage and the specific energy of the lithium ion battery that adopts this positive pole.Therefore, adopt LiNi 0.5Mn 1.5O 4Composite modification material is as the positive electrode active material material, technical recipe and electrode design by the advanced person, it is about 30% that the lithium ion battery specific energy that itself and carbon class negative pole form can improve, and has simultaneously good charge-discharge performance and cycle performance, is easy to large-scale industrial production.
Present embodiment provides a kind of high-voltage lithium ion batteries anodal, and this positive pole comprises collector, is coated in positive electrode active material material, conductive agent, binding agent on this collector,
Wherein the positive electrode active material material is 5V high voltage binary composite L iNi xMn 2-xO 4/ C (0<x≤0.5, Typical Representative chemical formula LiNi 0.5Mn 1.5O 4/ C and LiNi 0.4Mn 1.6O 4/ C),
Preferentially select LiNi 0.5Mn 1.5O 4/ C;
Anode formula is:
The positive active material of 85%-95% weight, the conductive agent of 2.5%-7.5% and the binding agent of 2.5%-7.5%,
Wherein the proportioning of conductive agent and binding agent use amount is (1.0-1.25): 1,
Anodal coated side density is 26mg/cm 2-35mg/cm 2
Present embodiment also provides a kind of lithium ion battery, this battery comprises positive pole, negative pole, is inserted in barrier film, electrolyte, battery case between positive pole and the negative pole, wherein said positive pole comprises collector, is coated in positive electrode active material material, binding agent, conductive agent on this collector, and wherein the positive electrode active material material is 5V high voltage binary composite L iNi xMn 2-xO 4/ C (0<x≤0.5, Typical Representative chemical formula LiNi 0.5Mn 1.5O 4/ C and LiNi 0.4Mn 1.6O 4/ C), preferentially select LiNi 0.5Mn 1.5O 4/ C; Anode formula is: the positive active material of 85%-95% weight, and the conductive agent of 2.5%-7.5% and the binding agent of 2.5%-7.5%, wherein the proportioning of conductive agent and binding agent use amount is (1.0-1.25): 1, anodal coated side density is 26mg/cm 2-35mg/cm 2
Present embodiment has the following advantages:
The lithium ion battery that present embodiment provides is compared with similar lithium ion battery product, has open circuit voltage height, discharge voltage plateau height, and specific energy is high, charge-discharge performance and good cycle; Anodal high voltage binary composite positive pole and the advanced technical recipe of adopting through the optimal design of electrode, can increase substantially lithium ion battery specific energy and volumetric specific energy simultaneously, saves volumetric spaces and weight.
This preferred embodiment provides a kind of high-voltage lithium ion batteries anodal, and this positive pole comprises collector, is coated in positive electrode active material material, binding agent, conductive agent on this collector, and wherein the positive electrode active material material is 5V high voltage binary composite L iNi xMn 2-xO 4/ C (0<x≤0.5, Typical Representative chemical formula LiNi 0.5Mn 1.5O 4/ C and LiNi 0.4Mn 1.6O 4/ C), preferentially select LiNi 0.5Mn 1.5O 4/ C.Anode formula is: the positive active material of 85%-95% weight, and the conductive agent of 2.5%-7.5% and the binding agent of 2.5%-7.5%, wherein the proportioning of conductive agent and binding agent use amount is (1.0-1.25): 1, anodal coated side density is 26mg/cm 2-35mg/cm 2
Described collector is aluminium foil, thickness 15 μ m-40 μ m.
Described binding agent is one or both the mixture in Kynoar, the polytetrafluoroethylene.
Described conductive agent is the hybrid conductive agent, is comprised of super conductive black and super electrically conductive graphite, and proportioning is 1: 1 (w: w).
The preparation method of described positive pole is
First binding agent is dispersed in the middle of the solvent,
Again with positive electrode active material material and conductive agent composition mixture, add in the container that passes into nitrogen or argon gas inert atmosphere, ball milling, fully to be ground and evenly mix after join in the middle of the solvent, mix and obtain slurry, prepared slurry is coated in above the collector aluminium foil, dry, roll, cut, can obtain above-mentioned positive pole.
Described solvent is 1-METHYLPYRROLIDONE.
The lithium ion battery that present embodiment provides, this battery comprise positive pole, negative pole, are inserted in barrier film, electrolyte, battery case between positive pole and the negative pole.Described barrier film is polyethylene, polypropylene or polyethylene and polypropylene composite film, is inserted in the middle of anodal and the negative pole.
Described negative pole can adopt the preparation method of lithium ion battery negative known in the art to make, and in general described negative pole comprises negative electrode active material, conductive agent, binding agent and collector.
Described negative electrode active material is one or more in native graphite, Delanium, carbonaceous mesophase spherules, hard carbon, ashbury metal, silicon alloy, Si-C composite material, 3 SiC 2/graphite composite material and the lithium titanate material, preferentially selects Delanium.Described binding agent is one or both the mixture in Kynoar (PVDF), polytetrafluoroethylene (PTFE), butadiene-styrene rubber (SBR), the sodium carboxymethylcellulose (CMC).Described conductive agent is one or more the mixture in acetylene black, super conductive black, super electrically conductive graphite, the conductive carbon nanotube.Described collector is Copper Foil or aluminium foil.
The preparation method of described negative pole is for being dispersed in binding agent first in the middle of the solvent, joins in the middle of the solvent after negative electrode active material material and conductive agent evenly being mixed again, and mixes, be coated in above the collector, drying rolls, cut, can obtain above-mentioned negative pole.Described solvent is deionized water or 1-METHYLPYRROLIDONE.
Described electrolyte is organic liquid electrolyte, and wherein the electrolyte lithium salt of electrolyte is LiPF 6, LiClO 4, LiBOB, LiBF 6, LiAsPF 6, LiCF 3SO 3, LiN (CF 3SO 2) 2, Li (C 2F 5) 3PF 3, Li (C 3F 7) 3PF 3A kind of mixture of or at least 2 kinds of salt; The solvent of electrolyte is the mixed system of a kind of or at least 2 kinds of solvents in ethylene carbonate, propene carbonate, dimethyl carbonate, carbonic acid diethyl ester, methyl ethyl carbonate, oxolane, the dioxolanes.
Described battery case is plastic casing, plastics and metallic composite shell, metal shell or metallic alloy shell.
Above-mentioned positive pole, negative pole, the barrier film that is inserted between positive pole and the negative pole are assembled, by fluid confluence lug and connecting terminals are connected together, in the battery case of packing into, and then injection electrolyte, sealing changes into, reprocessing can obtain the lithium ion battery of present embodiment.
Anodal and use the lithium ion battery of this positive pole to be elaborated to a kind of high-voltage lithium ion batteries of present embodiment below by instantiation.
Preferred embodiment example 1
This embodiment is anodal for the preparation of the high-voltage lithium ion batteries of present embodiment
By mass percentage, with 91% positive electrode active material material LiNi 0.5Mn 1.5O 4/ C, 2.5% the super carbon black of leading, 2.5% super electrically conductive graphite, 4% binding agent Kynoar as solvent, is dispersed in binding agent in the middle of the solvent with 1-METHYLPYRROLIDONE first; With conductive agent and positive electrode active material material mixing and stirring, be scattered in again in the middle of the solvent again, stir, make its even mixing, make slurry., as collector slurry evenly is coated on the aluminium foil with the thick aluminium foil of 19 μ m, the control temperature is 125 ℃ of dry 8h, and anodal coated side density is 31mg/cm 2
With pole piece roll, 115 ℃ of dry 12h under the inert argon atmosphere again, then cut, make positive pole.
Preferred embodiment example 2
This embodiment is anodal for the preparation of the high-voltage lithium ion batteries of present embodiment
By mass percentage, with 86% positive active material LiNi 0.5Mn 1.5O 4/ C material, 3.75% superconduction carbon black, 3.75% electrically conductive graphite, 6.5% binding agent Kynoar as solvent, is dispersed in binding agent in the middle of the solvent with 1-METHYLPYRROLIDONE first; With conductive agent and positive electrode active material material mixing and stirring, be scattered in again in the middle of the solvent again, stir, make its even mixing, make slurry., as collector slurry is coated on the aluminium foil with the thick aluminium foil of 25 μ m, the control temperature is 125 ℃ of dry 8h.The coated side density of positive electrode is 26mg/cm 2
With pole piece roll, 110 ℃ of dry 12h under the inert atmosphere of nitrogen environment again, then cut, make positive pole.
Preferred embodiment example 3
This embodiment is anodal for the preparation of the high-voltage lithium ion batteries of present embodiment
By mass percentage, with 94% positive active material LiNi 0.5Mn 1.5O 4/ C material, 1.5% superconduction carbon black, 1.5% electrically conductive graphite, 3% binding agent Kynoar as solvent, is dispersed in binding agent in the middle of the solvent with 1-METHYLPYRROLIDONE first; With conductive agent and positive electrode active material material mixing and stirring, be scattered in again in the middle of the solvent again, stir, make its even mixing, make slurry., as collector slurry is coated on the aluminium foil with the thick aluminium foil of 21 μ m, the control temperature is 125 ℃ of dry 8h.The coated side density of positive electrode is 35mg/cm 2
With pole piece roll, 110 ℃ of dry 12h under the inert atmosphere of nitrogen environment again, then cut, make positive pole.
Preferred embodiment example 4
This embodiment is for the preparation of lithium ion battery, and this lithium ion battery adopts the positive pole of the made present embodiment of embodiment 3.
By mass percentage, the negative electrode active material Delanium material with 88%, 4.0% superconduction carbon black, 4.0% electrically conductive graphite, 4% SBR and CMC hybrid adhesive take deionized water as solvent, are dispersed in binding agent in the middle of the solvent first; With conductive agent and negative electrode active material material mixing and stirring, be scattered in again in the middle of the solvent again, stir, make its even mixing, make slurry., as collector slurry is coated on the Copper Foil with the thick Copper Foil of 10 μ m, the control temperature is 110 ℃ of dry 8h.The coated side density of negative electrode is 14mg/cm 2
With pole piece roll, 105 ℃ of dry 12h under the inert atmosphere of nitrogen environment again, then cut, make negative pole.
Positive pole, negative pole, barrier film are assembled again, by fluid confluence lug and connecting terminals are connected together, in the battery case of packing into, and then inject electrolyte, sealing changes into, and reprocessing makes lithium ion battery.
The above has carried out exemplary description to the present invention by reference to the accompanying drawings; obviously specific implementation of the present invention is not subjected to the restriction of aforesaid way; as long as the various improvement of having adopted method design of the present invention and technical scheme to carry out; or directly apply to other occasion without improvement, all within protection scope of the present invention.

Claims (1)

1. the preparation method of a high-voltage lithium ion batteries positive pole is characterized in that, the high-voltage lithium ion batteries positive pole comprises collector, the positive electrode active material material, conductive agent and binding agent, wherein, described collector is aluminium foil, thickness 15 μ m-40 μ m, and the coated side density of described positive pole is 26mg/cm 2-35mg/cm 2Described positive electrode active material material is 5V high voltage binary composite L iNi 0.5Mn 1.5O 4/ C or LiNi 0.4Mn 1.6O 4/ C; Described positive electrode active material material, conductive agent and binding agent are according to the positive active material of weight proportion 85%-95%, and the conductive agent of 2.5%-7.5% and the binding agent of 2.5%-7.5% consist of slurry, and described slurry is coated on the described collector; Following steps are adopted in preparation:
(1) binding agent is dispersed in the middle of the solvent;
(2) with positive electrode active material material and conductive agent composition mixture, add in the container that passes into nitrogen or argon gas inert atmosphere;
(3) to the mixture ball milling, fully to be ground and evenly mix after join in the middle of the solvent, mix and obtain slurry;
(4) slurry is coated in above the collector aluminium foil, drying rolls, and cuts, and can obtain above-mentioned positive pole.
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