CN103811760B - A kind of lithium battery - Google Patents

A kind of lithium battery Download PDF

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Publication number
CN103811760B
CN103811760B CN201210439101.XA CN201210439101A CN103811760B CN 103811760 B CN103811760 B CN 103811760B CN 201210439101 A CN201210439101 A CN 201210439101A CN 103811760 B CN103811760 B CN 103811760B
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anode
negative electrode
thickness
battery
nanoscale
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CN103811760A (en
Inventor
李志坚
邓尧平
王小林
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INTELLECT PIONEERING BATTERY TECHNOLOGY Co Ltd
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INTELLECT PIONEERING BATTERY TECHNOLOGY Co Ltd
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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • 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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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

A kind of lithium battery, including battery container and anode, negative electrode and the electrolyte being placed in battery container, the polymeric separator plates of porous is had between anode and negative electrode, it is crucial that negative electrode is prepared by the transition metal intercalation active substance of lithiumation, nanoscale bentonite and carbon dust, anode is prepared by carbonaceous material, anode is 1: 1～1: 3 with the ratio of the thickness of negative electrode, the transition metal intercalation active substance of the described lithiumation in negative electrode, nanoscale bentonite and carbon dust are respectively 90～92%, 0.5～1.5% and 4～5% by weight, and surplus is PVDF.The invention has the beneficial effects as follows: the lithium ion battery prepared by above-mentioned structure, owing to the thickness of negative electrode is greatly reduced, the thickness of whole battery then can be greatly reduced.When also adding the nanoscale bentonite of trace in anode, also can improve receiving of lithium ion in anode, and the charging interval can be greatly reduced, its amplitude reduced is depending on the reduction amplitude of anode and the thickness of negative electrode.

Description

A kind of lithium battery
Technical field
The invention belongs to a kind of supply unit, be particularly a kind of chargeable lithium ion battery.
Background technology
Lithium ion battery has obtained increasingly extensive application, and the basic structure of lithium ion battery is to have anode and negative electrode, sun The polymeric barrier films of one porous is set between pole and cathode material, and by the electrode assemblie that obtains with a kind of non-containing lithium salts Aqueous electrolyte impregnates and prepares, and in such battery, during discharging, lithium ion, is then inserted by electrolyte from anode Entering negative electrode, during charging, the flowing of ion is reversible, and lithium ion passes through electrolyte from negative electrode, then as metallic lithium atoms Deposit back on anode；There is some problems the most to be solved, such as charging interval length (especially in above-mentioned lithium ion battery It is to large-scale dynamic lithium battery), relative to the thickness of anode, the thickness of negative electrode is relatively big and makes battery smart have any problem, when The defects such as the safety that so there is also other.
Summary of the invention
The goal of the invention of the present invention is the capacity by improving the insertable lithium ion of cathode material, and then it is little to realize battery Type or be more likely formed thinner battery.
The technical solution realizing the present invention is as follows: include battery container and the anode being placed in battery container, negative electrode And electrolyte, there is the polymeric separator plates of porous between anode and negative electrode, it is important to negative electrode is by the transition metal intercalation activity of lithiumation Prepared by material, nanoscale bentonite and carbon dust, anode is prepared by carbonaceous material, and anode is 1: 1～1 with the ratio of the thickness of negative electrode: 3。
The transition metal intercalation active substance of the described lithiumation in negative electrode, nanoscale bentonite and carbon dust are distinguished by weight Being 90～92%, 0.5～1.5% and 4～5%, surplus is PVDF.
The described lithiated transition metal intercalation active material in negative electrode includes selected from lithiated transition metal oxides, lithiumation Metal phosphate, lithiated cobalt oxides, LiCoO2、LiNiCoO2、LiAlNiCoO2、LiMnNiCoO2、LiMnO2、Li2Mn2O4With LiFe(PO4)6One or more compounds.
Described anode is 1: 1.5 or 1: 2 or 1: 2.5 with the ratio of the thickness of negative electrode.
Being provided with conductive support in described negative electrode, conductive support is Copper Foil or aluminium foil or other suitable metal, leads The thin shape thing of electric polymer.
The bentonitic particle diameter of described nanoscale is 5～50nm, and it is prepared by high speed shear method.
The carbonaceous material of described anode adds the nanoscale bentonite clay particle of by weight 0.2～0.5%, or institute The nanoscale bentonite clay particle stated processes through graphite material cladding.
Described nanoscale bentonite is negative one valency or negative bivalence or negative trivalent, or nanoscale bentonite is through organic process I.e. at the bentonitic brilliant Intercalation reaction organic ion of nanoscale.
Being provided with conductive support in described anode, conductive support is Copper Foil or aluminium foil or other suitable metal, leads The thin shape thing of electric polymer.
The lithium ion battery prepared by above-mentioned structure, owing to the thickness of negative electrode is greatly reduced, the thickness of whole battery is then Can be greatly reduced, owing to nanoscale bentonite has layer structure and has elecrtonegativity, its interlayer structure can be inserted into substantial amounts of Lithium ion, the lithiation level that can improve cathode material maybe can accommodate substantial amounts of lithium ion, and owing to the thickness of negative electrode reduces, machinery is strong Degree also can reduce, therefore can suitably increase the thickness of the conductive support in negative electrode；When the nanoscale also adding trace in anode is swollen During profit soil, also can improve receiving of lithium ion in anode, and the charging interval can be greatly reduced, its amplitude reduced regards anode Depending on the reduction amplitude of the thickness of negative electrode.
Accompanying drawing explanation
Fig. 1 is the local section schematic diagram of the present invention.
Detailed description of the invention
Referring to Fig. 1, Fig. 1 and only give the local structural graph of lithium ion battery so that the present invention to be described, other of battery does not has Having the part provided is prior art.Specific embodiments of the present invention include battery container 1 and the sun being placed in battery container 1 Pole 2, negative electrode 3 and nonaqueous electrolyte 4, have the polymeric separator plates 5 of porous between anode 2 and negative electrode 3, battery other portion due Dividing and the most no longer describe in detail for prior art such as cover plate, electrode ear and wire etc., the polymeric separator plates 5 of above-mentioned porous is also for existing skill Art, then has dividing plate 5 to isolate anode 2 and negative electrode 3 when battery uses the electrolyte of liquid, if electrolyte is solid polymer electricity Solve liquid, then as it is known in the art, may not include dividing plate 5 in battery, and solid electrolyte can be arranged in as shown in this field Between anode 2 and negative electrode 3.
Described anode 2 is made up of carbonaceous material, such as but not limited to graphite, coke, petroleum coke, carbon, partly or entirely Graphited carbon structure or any other agreeable carbonaceous material or carbon being inserted into lithium ion therein known in the art Structure, anode 2 can be coated above-mentioned carbonaceous material by the thin conductive material two sides as anode and constitute；Negative electrode 3 is Including the one side or or the electrochemical Iy active cathode material on preferred two sides, the active cathode material that are coated or attached to conductive supporting For the transition metal intercalation active substance of lithiumation, it includes selected from lithiated transition metal oxides, lithiated metal phosphate, lithiumation Cobalt/cobalt oxide, LiCoO2、LiNiCoO2、LiAlNiCoO2、LiMnNiCoO2、LiMnO2、Li2Mn2O4And LiFe(PO4)6One Or multiple compounds, during discharging, lithium ion by electrolyte, is inserted into negative electrode from anode, during charging, and lithium ion Flowing be reversible, lithium ion by electrolyte, then returns on anode as metallic lithium atoms or ion deposition from negative electrode, The capacity of battery depend on the thickness of male or female and male or female can the lithium ion of capacity, certainly also have the known of other Reason；In the present invention, nanoscale bentonite can make the lithium ion of insertion be significantly increased, and bentonite has special stratiform knot Structure, its crystal interlayer is elecrtonegativity, and between crystal layer, cation that is adsorbed or that insert can exchange, therefore between crystal layer adsorbable or Insert substantial amounts of lithium ion, to the absorption of low price cation or insert performance more preferably, the therefore lithiumation in above-mentioned negative electrode Transition metal intercalation active substance, nanoscale bentonite and carbon dust are respectively 90～92%, 0.5～1.5% and 4～5% by weight, Surplus is PVDF(polyvinylidene fluoride)；Due to according to the above ratio, adding bentonite in negative electrode, the insertable lithium ion of negative electrode is big Width increases, and therefore the thickness of negative electrode can significantly reduce, and the thickness of such as negative electrode is 1.5～3 times of anode thickness；Non aqueous electrolysis Liquid can be the solution of one or more lithium salts in organic nonaqueous solvent or solvent mixture, such as lithium salts can include but It is not limited to LiPF6、LiClO4、LiBF4Deng, solvent can include but not limited to PC(Allyl carbonate), EC(ethylene carbonate), DMC(dimethyl carbonate), DEC(carbonic acid diethyl ester) or suitable various mixed liquors in other this area, and lithium salts in electrolyte Concentration can be more than two times of normal concentration, and the gap between the crystal layer substantially having due to bentonite, for good porous Matter, then the increase that the bulk density of cathode material also can be suitable, not only add intensity but also reduce the thickness of negative electrode, such as can be by Bulk density increases by 10～15%；According to the difference of the male or female material to the difference of the requirement of battery performance and selection, sun Pole is 1: 1.8 or 1: 2 or 1: 2.5 with the ratio of the thickness of negative electrode, is the most successively to be charged from surface during battery charging, complete The time of charging is become to have the thickness the biggest then charging interval of direct relation, anode and negative electrode more with the thickness of male or female Long, the use of large-sized battery or power type is brought inconvenience by this, and therefore the above-mentioned technical characteristic of the present invention makes the thickness of negative electrode drop The low time being conducive to significantly shortening charging, through test, the charging interval is the 1/3～1/5 of prior art；Due to male or female Thickness reduce, then mechanical strength reduces accordingly, then be provided with conductive support in negative electrode, conductive support be Copper Foil or aluminium foil or Other suitable metal, the thin shape thing of conducting polymer, conductive support can strengthen the intensity of negative electrode and set negative electrode centre position, As long as its thickness can meet the technique in cell manufacturing process and support requires, such as between tens microns to hundreds of micron ?；About above-mentioned nanoscale bentonite, its particle diameter can be between 5～50nm, and it can be by high speed shear method system Standby (prior art), although the excessive preparation of its particle diameter is convenient, but the efficiency of receiving lithium ion or bulk density can drop Low, particle diameter is too small then because of character known to bentonite, and shearing difficulty and granule homogeneity are the most impacted；Due to swollen The profit elecrtonegativity that has of soil, it can be negative one valency or negative bivalence or negative trivalent, because of bentonitic electronegative difference, its interpolation The amount of the cation entered is the most different, for adapting to the needs of battery, bentonite can carry out organic process to reach modified Processing (such as elecrtonegativity) and improve stability, above-mentioned Organic Modification of Bentonites is the prior art of comparative maturity, its essence is At bentonitic brilliant Intercalation reaction organic ion, surface after deliberation, organic ion absorption on bentonitic bottom surface be all Orientations between crystal layer, so the expansion of crystal layer is minimum, in test, the cathode thickness of mensuration completes in charge or discharge Time, its thickness varies less, although this also further illustrates increasing lithium ion content, inserts containing in bentonitic cathode material An electropositive lithium ion part be contained between bentonitic crystal layer；Through test, added with by weight in the carbonaceous material of anode It is calculated as the nanoscale bentonite clay particle of 0.2～0.5%, is conducive to improving concentration or the content of lithium ion and suitably reducing thickness, also Be conducive to quick charging and discharging capabilities, through test, nanoscale bentonite clay particle processed through graphite material cladding, be conducive to improving Anode conducting rate, further charging and discharging capabilities.
For further appreciating that the present invention, provide the specific embodiment of the present invention in more detail.
Embodiment 1:
The anode material layer that anode is coated by Copper Foil and Copper Foil two sides is constituted, described anode material layer by graphite, PVDF or graphite, PVDF and the mixing of nanoscale bentonite are constituted, the composition of graphite and PVDF by weight 92% and 8%, or stone Ink, PVDF and the bentonitic composition of nanoscale by weight 90%, 9.7% and 0.3%；Cathode material is by LiNiCoO2Or LiAlNiCoO2、, carbon dust, nanoscale bentonite and PVDF(be respectively 90%, 4%, 1% and 5% by weight) mixing, be placed in The two sides of support member constitute negative electrode, and anode is 1: 2～2.5 with the thickness ratio of negative electrode；It is suitable to be provided with between the anode and the cathode Apertured polymeric film as dividing plate, such as can be selected for the polypropylene screen of porous；Anode, dividing plate and negative electrode can by this area The technology known is carried out around or be arranged in parallel composition column or tabular, then inserts in suitable shell, pour into electrolyte and Battery needed for the composition such as connection well known in the art, sealing, its specific capacity can reach 400～450mAh/g, and the charging interval is big Width is reduced to the 1/3～about 1/5 of general lithium battery.
Embodiment 2:
Anode is same as in Example 1 with the structure of negative electrode, and anode material is same as in Example 1, and cathode material is by LiMnO2、 Carbon dust, nanoscale bentonite and PVDF are respectively 90%, 4%, 1.5% and 4.5% by weight and are mixed with, anode and the thickness of negative electrode Degree ratio is 1: 2, and after measured, the Capacity Ratio of battery can reach 450～490mAh/g, and the charging interval is also greatly reduced, and structure is more Lightly.
Described in present invention book as described above and embodiment, reduce the thickness of anode and negative electrode, can the production cost of battery, While reducing the thickness of battery, reduce the charging interval, be more beneficial for the preparation of large-scale electrokinetic cell.

Claims (3)

1. a lithium battery, including battery container and the anode, negative electrode and the electrolyte that are placed in battery container, anode and negative electrode it Between have the polymeric separator plates of porous, it is characterised in that the structure of negative electrode is to be provided with cathode material in conductive support two sides, Cathode material is prepared by lithiated transition metal intercalation active material, nanoscale bentonite, carbon dust and PVDF, and anode also has conduction Support member and anode material are prepared by carbonaceous material, and anode is 1: 1～1: 3 with the ratio of the thickness of negative electrode, at described cathode material In, lithiated transition metal intercalation active material, nanoscale bentonite and carbon dust are respectively 90～92%, 0.5～1.5% by weight With 4～5%, surplus is PVDF, and the bentonitic particle diameter of described nanoscale is 5～50nm, and it is by high speed shear method system Standby, described nanoscale bentonite clay particle processes through graphite material cladding.
Lithium battery the most according to claim 1, it is characterised in that: the lithiated transition metal intercalation in described cathode material Active substance is selected from LiCoO2Or LiMnO2。
Lithium battery the most according to claim 2, it is characterised in that: described anode is 1: 1.5 with the ratio of the thickness of negative electrode Or 1: 2 or 1: 2.5.
CN201210439101.XA 2012-11-07 2012-11-07 A kind of lithium battery Active CN103811760B (en)

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CN103811760B true CN103811760B (en) 2016-08-10

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101202345A (en) * 2006-09-11 2008-06-18 株式会社Lg化学 Electrode material including clay mineral and electrochemical cell employed with the same
CN101719548A (en) * 2009-11-05 2010-06-02 翟东军 Compound lithium iron phosphate used as positive pole material of lithium ion battery and preparation method thereof
CN101777642A (en) * 2010-01-29 2010-07-14 天津大学 Lithium secondary battery cathode material and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3587935B2 (en) * 1996-05-16 2004-11-10 Ｔｄｋ株式会社 Lithium secondary battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101202345A (en) * 2006-09-11 2008-06-18 株式会社Lg化学 Electrode material including clay mineral and electrochemical cell employed with the same
CN101719548A (en) * 2009-11-05 2010-06-02 翟东军 Compound lithium iron phosphate used as positive pole material of lithium ion battery and preparation method thereof
CN101777642A (en) * 2010-01-29 2010-07-14 天津大学 Lithium secondary battery cathode material and preparation method thereof

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