CN100502100C - Lithium secondary anode, its preparing method and lithium secondary anode using same - Google Patents

Lithium secondary anode, its preparing method and lithium secondary anode using same Download PDF

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CN100502100C
CN100502100C CNB2005100370211A CN200510037021A CN100502100C CN 100502100 C CN100502100 C CN 100502100C CN B2005100370211 A CNB2005100370211 A CN B2005100370211A CN 200510037021 A CN200510037021 A CN 200510037021A CN 100502100 C CN100502100 C CN 100502100C
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lithium secondary
secondary battery
different
lithium
compound
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CN1925191A (en
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何纪壮
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Hongfujin Precision Industry Shenzhen Co Ltd
Hon Hai Precision Industry Co Ltd
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Hongfujin Precision Industry Shenzhen Co Ltd
Hon Hai Precision Industry Co Ltd
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

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Abstract

This invention provides one lithium secondary battery anode and its process method, which comprises secondary anode composed of one base and two different compounds coating on different areas. The process method comprises the following steps: coating one compound onto anode base surface area different to basic materials; coating other compound different to basic materials on other part of the base surface to get lithium secondary battery anode of different basic material two compounds. This invention provides one lithium secondary battery composed of one anode, one cathode and one transmission isolation film.

Description

Cathode plate for lithium secondary battery, its preparation method and adopt this anodal lithium secondary battery
[technical field]
The present invention relates to a kind of lithium secondary battery, relate in particular to a kind of cathode plate for lithium secondary battery, its preparation method and adopt this anodal lithium secondary battery.
[background technology]
Lithium secondary battery is meant by lithium ion as conductive medium in the electrolyte, and the electro-chemical systems that can repeat to discharge and recharge.Along with the electronic product trend is compact, and environmental protection cry day is high, and lithium secondary battery is because of having high-energy-density, high-output power, quickly-chargeable, in light weight, volume is little and characteristic such as pollution-free, has become one of optimal selection of Portable 3C Product power supply supply.
Generally speaking, lithium secondary battery comprises a positive pole, a negative pole and connects anodal with negative pole and with the two separated osmotic isolating film.Above-mentioned positive pole, negative pole and osmotic isolating film place in the metal can, and inject the electrolyte in the metal can, soak anodal, negative pole, so that electrochemical reaction to take place, electric energy and chemical energy are changed mutually.
Wherein, osmotic isolating film is a loose structure, and ion is passed through, and but to electronic isolation, is generally polyethylene, polypropylene or polystyrene.Positive pole is the electronics provider, and the atom of positive electrode becomes ion in oxidizing process, and discharges electronics, and ion reduces at negative pole by osmotic isolating film, and electronics then transfers to and forms electric current in the external circuit.But negative material is generally lithium intercalation compound, comprises graphite, carbon fiber and metal oxide etc. as various material with carbon elements.
At present the positive electrode material of lithium secondary cell research emphasis is the positive electrode of Li-M-O (M is any one or two kinds of above compound of Co, Mn, Ni, Cr) system.Wherein, spinel-type LiMn 2O 4With its aboundresources, cheap, advantage such as pollution-free and synthetic method is simple becomes the focus of research, is considered to the positive electrode of tool potentiality in the lithium secondary battery.But, spinel-type LiMn 2O 4Cycle performance poor, charge/discharge capacity decay was serious when capacity attenuation, particularly temperature were higher than 55 ℃.Therefore, the research emphasis of Li-M-O compound positive electrode is to improve aspects such as charge/discharge capacity and cycle characteristics at present.
In order to improve the characteristic of positive electrode material of lithium secondary cell, the technology that is adopted mainly is that anodal material surface is carried out modification in recent years, thereby overcomes its capacity attenuation and improve chemical property.
But, all only adopt the unification compound that positive electrode is carried out finishing at present, though these class methods have been stablized the cycle performance of positive electrode, often be attended by the defective that initial capacity descends.
In view of this, a kind of cycle characteristics that can improve positive electrode material of lithium secondary cell is provided, can effectively stops simultaneously cathode plate for lithium secondary battery that initial capacity descends and preparation method thereof again and have a good lithium secondary battery of high-capacitance, high-temperature cycle life real for necessary.
[summary of the invention]
Below will a kind of cycle characteristics that can improve positive electrode material of lithium secondary cell be described, and can effectively stop lithium secondary battery positive active material of initial capacity decline and preparation method thereof simultaneously again with embodiment.
And, provide a kind of have high power capacity, the good lithium secondary battery of high-temperature cycle life by these embodiment.
This kind lithium secondary battery positive active material, comprise a base material and the two kinds of different compounds that are different from substrate material that apply in the zones of different on this base material part surface respectively, this base material is a kind of of cobalt acid lithium, lithium nickelate, LiMn2O4 and their modified compound; These two kinds of compound molecule formulas are respectively LiMO 2And A xO y, wherein, M is a kind of in Co, Ni, Mn, the Cr transition metal, and A is any in Mg, Sn, Al, the Si element, and x is 0<x≤2, and y is 0<y≤3.
The preparation method of this kind lithium secondary battery positive active material, its step comprises:
Applying the molecular formula that is different from substrate material on the base material part surf zone of lithium secondary battery positive active material is LiMO 2A compound, this base material is a kind of of cobalt acid lithium, lithium nickelate, LiMn2O4 and their modified compound, M is a kind of in Co, Ni, Mn, the Cr transition metal in the formula, obtains the base material part surf zone and is coated with LiMO 2Cathode plate for lithium secondary battery;
Applying the molecular formula that is different from substrate material on the other subregion of the substrate surface of lithium secondary battery positive active material is A xO yAnother compound, A is any in Mg, Sn, Al, the Si element in the formula, x is 0<x≤2, y is 0<y≤3, the zones of different that obtains the base material part surface is coated with the compound L iMO that is different from substrate material respectively 2And A xO yLithium secondary battery positive active material.
This kind lithium secondary battery comprises a positive pole, a negative pole and an osmotic isolating film, and this osmotic isolating film connects positive pole and separates with negative pole and with the two; The zones of different on the base material part surface of this positive electrode active materials is coated with two kinds of different compounds that are different from substrate material, and this base material is a kind of of cobalt acid lithium, lithium nickelate, LiMn2O4 and their modified compound; These two kinds of compound molecule formulas are respectively LiMO 2And A xO yWherein M is a kind of in Co, Ni, Mn, the Cr transition metal, and A is any in Mg, Sn, Al, the Si element, and the span of x, y is respectively 0<x≤2,0<y≤3.
Compared with prior art, lithium secondary battery positive active material of the embodiment of the invention and preparation method thereof, its advantage is: owing to be coated with two kinds of different compound L iMO that are different from substrate material in positive electrode active materials substrate surface zones of different 2And A xO y, wherein, LiMO 2Can between anodal base material and electrolyte, form one deck passivation layer, can reduce electrolytical decomposition, thereby make positive pole show good cyclic reversibility; A xO yCan form the high concentration metal atomic layer at anodal substrate surface, can reduce the dissolving of anodal crystal defect and minimizing cathode metal ion, thereby anodal high temperature cyclic performance is stablized, can also suppress the decay of anodal initial capacity.Thereby the cathode plate for lithium secondary battery of gained not only improves the charge of positive electrode, can also effectively stop the decay of capacitance simultaneously.
Adopt the advantage of this anodal lithium secondary battery to be: lithium secondary battery positive active material substrate surface zones of different is coated with two kinds of different compound L iMO that are different from substrate material 2And A xO y, can improve the charge of positive electrode, improve battery capacity and high-temperature cycle.
[description of drawings]
Fig. 1 be in the embodiment of the invention base material part surf zone by cathode plate for lithium secondary battery structural representation that lithium and cobalt oxides coated.
Fig. 2 is the cathode plate for lithium secondary battery structural representation that is coated on the substrate surface zones of different in the embodiment of the invention by cobalt lithium oxide and two kinds of compounds of magnesium oxide respectively.
Fig. 3 is a lithium secondary battery structural representation in the embodiment of the invention.
[embodiment]
The cathode plate for lithium secondary battery that the embodiment of the invention provided comprises a base material, and the two kinds of different compounds that are different from substrate material that apply in this substrate surface zones of different respectively; These two kinds of compound molecule formulas are respectively LiMO 2And A xO yWherein M is a kind of in Co, Ni, Mn, the Cr transition metal, and A is any in Mg, Sn, Al, the Si element, and the span of x, y is respectively 0<x≤2,0<y≤3.
In the present embodiment, M is Co; A is Mg.
Wherein said base material is a kind of of cobalt acid lithium, lithium nickelate, LiMn2O4 and their modified compound, and present embodiment adopts LiMn2O4 (LiMn 2O 4).
The preparation method of this kind cathode plate for lithium secondary battery that the embodiment of the invention provided, it may further comprise the steps:
Apply a compound that is different from substrate material on cathode plate for lithium secondary battery base material part surf zone, this compound molecule formula is LiMO 2, M is a kind of in Co, Ni, Mn, the Cr transition metal in the formula, obtains the base material part surf zone and is coated with LiMO 2Cathode plate for lithium secondary battery;
Apply another compound that is different from substrate material on the other subregion of cathode plate for lithium secondary battery substrate surface, this compound molecule formula is A xO y, A is any in Mg, Sn, Al, the Si element in the formula, and x is 0<x≤2, and y is 0<y≤3, obtains the substrate surface zones of different and is coated with the compound L iMO that is different from substrate material respectively 2And A xO yCathode plate for lithium secondary battery.
Wherein, coating compound LiMO 2And A xO yThe time, all can adopt solid-phase synthesis, gel-sol method or utilize K 3Fe (CN) 6The method that adsorption capacity applies, present embodiment applies LiMO 2Shi Liyong K 3Fe (CN) 6Adsorption capacity apply; Apply A xO yThe Shi Caiyong sol-gel process applies.
The present embodiment first step is with spinelle phase LiMn 2O 4Powder is anodal base material, utilizes K 3Fe (CN) 6Chemical adsorption capacity, with Co (NO 3) 2Solution slowly mixes the formation cobalt complex, controls reactant consumption and concentration therebetween, guarantees the cobalt complex precipitation and covers LiMn 2O 4On the positive pole powder part surface zone, obtain the positive pole that the base material part surf zone is coated by cobalt lithium oxide through heat treatment;
Second step was to utilize the product of sol-gel process with first step gained, with Mg (OH) 2Solution mixes, heat this mixture at a certain temperature, make the magnesium oxide of generation be coated on the zone that anodal substrate surface is not coated by cobalt lithium oxide, heat-treat the cathode plate for lithium secondary battery that obtains being coated on respectively the substrate surface zones of different afterwards again by cobalt lithiated compound and magnesium oxide.
The concrete steps of present embodiment are as follows:
(1) with the 10g particle diameter is 25 μ m base material powder LiMn 2O 4With 40mL concentration be the K of 0.1mol/L 3Fe (CN) 6Aqueous solution obtains solution A; With 2mL/min speed is the Co (NO of 0.05mol/L with 100mL concentration 3) 2Solution splashes into and obtains solution B in the solution A; Filtering solution B removes unnecessary K 3Fe (CN) 6With KNO 3Solution; With filtering gains and 100mL concentration is that the LiOH solution of 0.05mol/L fully mixes, and stirs 0.5 hour, obtains solution C; Refilter solution C, remove unnecessary LiOH solution; Wet mash after filtering was placed 90~100 ℃ of baking ovens dry 12 hours; Take out the material of oven dry, be placed under the oxygen state,, be calcined to 500 ℃, be incubated 10 hours, reduce to room temperature with the rate of temperature fall of 5 ℃ of per minutes again, obtain the positive pole that anodal base material part surf zone is coated by cobalt lithium oxide with the rate of heat addition of 5 ℃ of per minutes;
(2) anodal base material part surf zone is coated with the positive pole of cobalt lithium oxide and the Mg (OH) that 60mL concentration is 0.1mol/L 2Solution mixes; 200~300 ℃ of heating, make by Mg (OH) 2The magnesium oxide that decomposes gained is coated on the zone that described substrate surface is not coated by cobalt lithium oxide; Carry out calcination at 750 ℃ and handled 12 hours, obtain being coated on respectively the positive pole of substrate surface zones of different by cobalt lithium oxide and two kinds of compounds of magnesium oxide.
Fig. 1 be in the present embodiment base material part surf zone by cathode plate for lithium secondary battery structural representation that lithium and cobalt oxides coated, wherein, lithium and cobalt oxides 14 is coated on base material 12 part surface zones, forms to have only a kind of compound local surfaces to modify cathode plate for lithium secondary battery structure 10.
Fig. 2 is the cathode plate for lithium secondary battery structural representation that is coated on the substrate surface zones of different in the present embodiment by cobalt lithium oxide and two kinds of compounds of magnesium oxide respectively, wherein, lithium and cobalt oxides 14 and magnesium oxide 21 are coated on the zones of different of substrate surface respectively, form two kinds of different compound finishing cathode plate for lithium secondary battery structures 20.
See also Fig. 3, the lithium secondary battery 100 of present embodiment comprises a positive pole 110, a negative pole 120 and connects anodal 110 with negative pole 120 and with the two separated osmotic isolating film 130.This osmotic isolating film 130 is loose structures, and ion is passed through, and but to electronic isolation, is generally polyethylene, polypropylene or polystyrene, adopts polyethylene in the present embodiment.But the material of negative pole 120 is a lithium intercalation compound, comprises graphite, carbon fiber and metal oxide etc. as various material with carbon elements, adopts graphite in the present embodiment.The substrate surface zones of different of present embodiment cathode plate for lithium secondary battery 110 is coated with two kinds of different compound cobalt lithium oxides and the magnesium oxide that is different from substrate material.
The operation principle of present embodiment lithium secondary battery 100 is: the atom of cathode plate for lithium secondary battery 110 becomes ion in oxidizing process, and discharges electronics, and in another electrode reduction, electronics then transfers to and forms electric current in the external circuit ion by osmotic isolating film 130.
Present embodiment cathode plate for lithium secondary battery and preparation method thereof provides a kind of cathode plate for lithium secondary battery by cobalt lithium oxide and two kinds of compound finishinges of magnesium oxide, because lithium and cobalt oxides can form one deck passivation layer between anodal base material and electrolyte, can reduce electrolytical decomposition, thereby make positive pole show good cyclic reversibility; Magnesium oxide can form the high concentration metal atomic layer at anodal substrate surface, can reduce the dissolving of anodal crystal defect and minimizing cathode metal ion, thereby anodal high temperature cyclic performance is stablized, and can also suppress the decay of anodal initial capacity.Thereby the cathode plate for lithium secondary battery of gained not only improves the charge of positive electrode, can also effectively stop the decay of capacitance simultaneously.Adopt this anodal lithium secondary battery to have high-capacitance, the good advantage of high-temperature cycle life.

Claims (9)

1. lithium secondary battery positive active material, comprise a base material, this base material is a kind of of cobalt acid lithium, lithium nickelate, LiMn2O4 and their modified compound, it is characterized in that this lithium secondary battery positive active material also comprises two kinds of different compounds that are different from substrate material, it is coated in the zones of different on this base material part surface respectively, and these two kinds of compound molecule formulas are respectively LiMO 2And A xO y, wherein M is a kind of in Co, Ni, Mn, the Cr transition metal, A is any in Mg, Sn, Al, the Si element, and the span of x, y is respectively 0<x≤2,0<y≤3.
2. the preparation method of a lithium secondary battery positive active material, its step comprises:
Applying the molecular formula that is different from substrate material on lithium secondary battery positive active material base material part surf zone is LiMO 2A compound, this base material is a kind of of cobalt acid lithium, lithium nickelate, LiMn2O4 and their modified compound, M is a kind of in Co, Ni, Mn, the Cr transition metal in the formula, obtains the base material part surf zone and is coated with LiMO 2Cathode plate for lithium secondary battery; Applying the molecular formula that is different from substrate material on the other subregion of lithium secondary battery positive active material substrate surface is A xO yAnother compound, A is any in Mg, Sn, Al, the Si element in the formula, and the span of x, y is respectively 0<x≤2,0<y≤3, the zones of different that obtains the base material part surface is coated with the compound L iMO that is different from substrate material respectively 2And A xO yLithium secondary battery positive active material.
3. as the preparation method of lithium secondary battery positive active material as described in the claim 2, it is characterized in that coating compound LiMO 2The time, adopt solid-phase synthesis, gel-sol method or utilize K 3Fe (CN) 6The method that applies of adsorption capacity.
4. as the preparation method of lithium secondary battery positive active material as described in the claim 2, it is characterized in that coating compound A xO yThe time, adopt solid-phase synthesis, gel-sol method or utilize K 3Fe (CN) 6The method that applies of adsorption capacity.
5. lithium secondary battery, comprise a positive pole, a negative pole and an osmotic isolating film, this osmotic isolating film connects positive pole and separates with negative pole and with the two, it is characterized in that: the zones of different on this lithium secondary battery positive active material base material part surface is coated with two kinds of different compounds that are different from substrate material, and this base material is a kind of of cobalt acid lithium, lithium nickelate, LiMn2O4 and their modified compound; These two kinds of compound molecule formulas are respectively LiMO 2And A xO yWherein M is a kind of in Co, Ni, Mn, the Cr transition metal, and A is any in Mg, Sn, Al, the Si element, and the span of x, y is respectively 0<x≤2,0<y≤3.
6. lithium secondary battery as claimed in claim 5 is characterized in that described osmotic isolating film is a loose structure.
7. lithium secondary battery as claimed in claim 5, the material that it is characterized in that described osmotic isolating film is polyethylene, polypropylene or polystyrene.
8. lithium secondary battery as claimed in claim 5, but it is characterized in that the material of described negative pole is lithium intercalation compound.
9. lithium secondary battery as claimed in claim 8, but it is characterized in that described lithium intercalation compound is graphite, carbon fiber or metal oxide.
CNB2005100370211A 2005-09-02 2005-09-02 Lithium secondary anode, its preparing method and lithium secondary anode using same Expired - Fee Related CN100502100C (en)

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JP5568886B2 (en) * 2009-05-07 2014-08-13 ソニー株式会社 Active material, battery and method for producing electrode
CN104078655B (en) * 2014-06-30 2016-03-09 天津巴莫科技股份有限公司 A kind of preparation method of cladded type titanium oxygen compound
CN109911946B (en) * 2017-12-13 2020-10-16 中国科学院过程工程研究所 Method for recycling waste sagger in preparation process of lithium cobaltate battery material

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Publication number Priority date Publication date Assignee Title
US20010031311A1 (en) * 2000-04-17 2001-10-18 Lee Jai Young Method for surface treatment of lithium manganese oxide for positive electrode in lithium secondary battery
US20020055042A1 (en) * 2000-03-13 2002-05-09 Kweon Ho-Jin Positive active material for rechargeable lithium battery and method of preparing same
CN1416189A (en) * 2001-11-02 2003-05-07 中国科学院物理研究所 Lithium secondary battery by use of composite material covered with nano surface as active material of positive polar
CN1585161A (en) * 2004-05-25 2005-02-23 惠州Tcl金能电池有限公司 Potassium manganate modifying technology of secondary lithium ion battery
CN1627550A (en) * 2003-12-11 2005-06-15 比亚迪股份有限公司 Anode material of lithium ion cell and preparation method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020055042A1 (en) * 2000-03-13 2002-05-09 Kweon Ho-Jin Positive active material for rechargeable lithium battery and method of preparing same
US20010031311A1 (en) * 2000-04-17 2001-10-18 Lee Jai Young Method for surface treatment of lithium manganese oxide for positive electrode in lithium secondary battery
CN1416189A (en) * 2001-11-02 2003-05-07 中国科学院物理研究所 Lithium secondary battery by use of composite material covered with nano surface as active material of positive polar
CN1627550A (en) * 2003-12-11 2005-06-15 比亚迪股份有限公司 Anode material of lithium ion cell and preparation method
CN1585161A (en) * 2004-05-25 2005-02-23 惠州Tcl金能电池有限公司 Potassium manganate modifying technology of secondary lithium ion battery

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