CN100413139C - Lithium secondary cell using boride as negative polar material - Google Patents

Lithium secondary cell using boride as negative polar material Download PDF

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CN100413139C
CN100413139C CNB200610083254XA CN200610083254A CN100413139C CN 100413139 C CN100413139 C CN 100413139C CN B200610083254X A CNB200610083254X A CN B200610083254XA CN 200610083254 A CN200610083254 A CN 200610083254A CN 100413139 C CN100413139 C CN 100413139C
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lithium secondary
secondary battery
negative
metal boride
boride
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CN1851970A (en
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吴川
吴锋
白莹
单忠强
董力伟
王鑫
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NATIONAL HIGH-TECHNOLOGIES GREEN MATERIALS DEVELOPMENT CENTER
Beijing Institute of Technology BIT
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NATIONAL HIGH-TECHNOLOGIES GREEN MATERIALS DEVELOPMENT CENTER
Beijing Institute of Technology BIT
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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
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    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract

The present invention belongs to the technical field of a high energy battery, which provides a lithium secondary battery using a boride as negative pole materials. The lithium secondary battery provided by the present invention is composed of a negative pole, a positive pole, a membrane, electrolyte or polymer electrolyte, wherein the positive pole and the negative pole are respectively coated on a current collecting pole and are connected with both ends of a battery case mutually insulated through the current collecting pole, the negative pole is composed of the boride, an agglomerant and a conductive agent, and active materials of the negative pole are borides. The chemical composition of the borides is MaBbOc, and M is selected from one kind of or many kinds of Co, Al, Zr, V, Cr, Ni, Fe, Ti, Cu, Zn, Nd, Mo, Ag, Mg; 1</=a</=4, 0</=b</= 1, 0</=c</=4; the structural form of the borides is in a crystalline state or in a non-crystalline state. The lithium secondary battery of the present invention has the advantages of high capacity, no environmental pollution and safe use and is suitable for various small-sized movable electronic apparatuses.

Description

A kind of is the lithium secondary battery of negative material with the boride
Technical field
The invention belongs to the technical field of high-energy battery technical field, particularly lithium secondary battery, providing a kind of is the lithium secondary battery of negative material with the metal boride.
Technical background
At present, high energy secondary cell technology develops rapidly, no matter as " replacement technique " or " transitional technology ", all will occupy critical positions (look into full property, chemical power source selects opinion, publishing house of Wuhan University, Wuhan, 2005) in the energy resource structure in future; And lithium secondary battery is the important member in the high energy secondary cell.Want to continue to improve the energy density and the power density of lithium secondary battery, very important one side is exactly to develop high performance electrode material.
Because lithium metal has the high-energy-density of 3830mAh/g, and be used as the negative material of lithium secondary battery the earliest, but the part Li dendrite that forms in circulation can pierce through barrier film and cause soft short circuit, do you cause safety problem (B.Scrosati.Lithium RockingChair Batteries:An Old Concept? .J.Electrochem.Soc, 1992,139:2776～2780).When the negative material of initial searching substituted metal lithium, people have selected the alloy of lithium naturally.Because the lithium alloy negative pole has been avoided the growth of Li dendrite, the fail safe that has improved battery causes researcher's extensive concern; But often experiencing bigger volume and morphology change in the cyclic process repeatedly, electrode material efflorescence gradually lost efficacy, and alloy structure is destroyed.The theoretical embedding lithium capacity of the graphite-like material with carbon element that extensively adopts in the commercialization lithium secondary battery is 372mAh/g at present, is difficult to satisfy the demand that people improve constantly the high energy secondary cell; Study and some oxides, sulfide, nano metal, metal alloy, nano-carbon material etc. all are taken as the negative material of lithium secondary battery, but all also have suitable distance from commercialization.What we were nearest discovers, some borides are doff lithium reversibly, and its embedding lithium capacity surpassed the theoretical embedding lithium capacity of graphite-like material with carbon element, can be used as the new lithium secondary battery cathode material of a class.
Summary of the invention
The object of the present invention is to provide a kind of is the lithium secondary battery of negative material with the metal boride.The metal boride cathode material preparation method of this lithium secondary battery is flexible and varied, the preparation process simple and fast, and have very high electro-chemical activity, thereby this lithium secondary battery can be realized very high capacity.
For achieving the above object, provided by the present invention is that the lithium secondary battery of negative material material comprises negative pole, positive pole, barrier film, electrolyte or polymer dielectric with the metal boride on forming; Positive pole includes the transition metal oxide that contains lithium, or li-contained phosphate, or lithium metal; Separate by barrier film that has soaked electrolyte or polymer dielectric between positive pole and the negative pole; Positive electrode active material and negative electrode active material are coated in afflux respectively and extremely go up, and link to each other with the battery case two ends of mutually insulated by the afflux utmost point; Negative pole is made up of metal boride, binding agent and conductive agent, and used negative active core-shell material is a metal boride.
Provided by the invention is that the chemical composition of used metal boride is M in the lithium secondary battery of negative material material with the metal boride aB bO cWherein M is selected from one or more among Co, Al, Zr, V, Cr, Ni, Fe, Ti, Cu, Zn, Nd, Mo, Ag, the Mg;
1≤a in the described metal boride≤4,0.04≤b≤1,0≤c≤4;
The structural form of described metal boride is crystalline state or amorphous state;
The preparation process of described metal boride is simple, and approach is various, and it is synthetic to pass through solwution method, roasting method, ball-milling method, reducing process, the precipitation method.
Provided by the invention is that used binding agent is selected from one or more in Kynoar, polytetrafluoroethylene, polyacrylate, methylcellulose, polymethacrylates, polyvinyl alcohol, the vinylidene fluoride-hexafluoropropylene copolymer in the lithium secondary battery of negative material with the metal boride;
Used conductive agent is selected from one or more in acetylene black, graphite, carbonaceous mesophase spherules, metal powder, the alloyed powder;
When used metal boride possesses enough good conductivity, also can not use conductive agent in the negative pole;
Used negative pole currect collecting is a kind of in wire netting, metal forming, carbon cloth, carbon paper, the nickel foam very.
The good effect that the present invention possessed has:
1, the preparation method of described metal boride is flexible and varied, the preparation process simple and fast.
2, key component such as general barrier film, electrolyte has good compatibility in described metal boride and the commercial lithium secondary battery, can be assembled into battery product at an easy rate.
What 3, provided is that the lithium secondary battery of negative material has very high capacity with the metal boride, and environmentally safe is safe and reliable.
Description of drawings
Accompanying drawing-for pressing first three all charging and discharging curve figure of the prepared lithium secondary battery of embodiment 1,
Wherein transverse axis is represented capacity, and unit is mAh/g; Longitudinal axis representative voltage, unit is V.
Embodiment
Describe content of the present invention in detail below by specific embodiment:
Embodiment 1
Get the CoCl of 1mol/l 2Solution 200ml places flask, is the NaBH of 2mol/l then with 230ml concentration 4Solution joins in the flask; In this process, the solution in the flask is carried out mechanical agitation.After reaction finishes, stop stirring and make the suspension-turbid liquid layering.Supernatant liquor is removed; The lower sediment thing is taken out,, in eluate, drip AgNO with deionized water wash, suction filtration 3Solution no longer produces white precipitate.The sediment that above-mentioned suction filtration is crossed obtains boride after 100 ℃ of following vacuumize, through inducing the coupling plasma spectroscopy, consist of Co 2.12B 1.03O 3.72
The negative pole preparation method who with the boride is active matter is as follows: with above-mentioned synthetic boride, mix as the polytetrafluoroethylene of the binding agent mass ratio with 85: 15, do not add conductive agent, compacting in flakes on as the nickel screen of the afflux utmost point.
The negative pole cutting for preparing is in blocks, and be assembled into Experimental cell with homemade Kynoar-hexafluoropropylene barrier film, metal lithium sheet, electrolyte adopts 1M LiPF 6-EC/DEC (vol 1: 1).Experimental cell is after ageing in 12 hours, with 0.05mA/cm 2Current density carry out charge-discharge test, discharge cut-off voltage is 0.005V, the charging cut-ff voltage is 2V.Its first discharge capacity reach 614mAh/g, surpassed the theoretical embedding lithium capacity of graphite-like material with carbon element, and had excellent cycle performance.The all charging and discharging curves of first three of Experimental cell as shown in drawings.
Embodiment 2
Get the NiCl of 0.2mol/l 2Solution 300ml places flask, is the NaBH of 0.5mol/l then with 200ml concentration 4Solution joins in the flask; In this process, the solution in the flask is carried out magnetic agitation.After reaction finishes, stop stirring and make the suspension-turbid liquid layering.Supernatant liquor is removed; The lower sediment thing is taken out,, in eluate, drip AgNO with deionized water wash, suction filtration 3Solution no longer produces white precipitate.The sediment that above-mentioned suction filtration is crossed continues 700 ℃ of heating 0.5 hour down after 90 ℃ of following vacuumize, after the cooling boride, through inducing the coupling plasma spectroscopy, consist of Ni 396B 0.04O 0.01
The negative pole preparation method who with the boride is active matter is as follows: with above-mentioned synthetic boride, as the N-methyl pyrrolidone solution of the Kynoar of binding agent, mix as the Ni powder of the conductive agent mass ratio with 80: 5: 15, be modulated into slurry, evenly be coated on the Copper Foil as the afflux utmost point, and oven dry.
The negative pole cutting for preparing is in blocks, and with commercial
Figure C20061008325400051
2300 barrier films, metal lithium sheet are assembled into Experimental cell, and electrolyte adopts 1M LiClO 4-EC/DMC (vol 1: 1).Experimental cell is after ageing in 12 hours, with 0.02mA/cm 2Current density carry out charge-discharge test, discharge cut-off voltage is 0.005V, the charging cut-ff voltage is 2V.Its first discharge capacity reach 412mAh/g, surpassed the theoretical embedding lithium capacity of graphite-like material with carbon element, and had excellent cycle performance.
Embodiment 3
Get 2.92 gram metal Fe, 3.02 gram metal M g, 1.23 gram B mix the back and place ball grinder under nitrogen atmospheres, and ball milling after 50 hours takes out product.Through inducing the coupling plasma spectroscopy, consist of Fe 1.02Mg 2.13B 0.82
The negative pole preparation method who with the boride is active matter is as follows: with above-mentioned synthetic boride, as the N-methyl pyrrolidone solution of the Kynoar of binding agent, mix as the Co powder of the conductive agent mass ratio with 80: 10: 10, be modulated into slurry, evenly be coated on the Copper Foil as the afflux utmost point, and oven dry.
The negative pole cutting for preparing is in blocks, and with commercial
Figure C20061008325400061
2300 barrier films, metal lithium sheet are assembled into Experimental cell, and electrolyte adopts 1M LiPF 6-EC/DMC (vol 1: 1).Experimental cell is after ageing in 8 hours, with 0.01mA/cm 2Current density carry out charge-discharge test, discharge cut-off voltage is 0.005V, the charging cut-ff voltage is 2V.Its first discharge capacity reach 394mAh/g, surpassed the theoretical embedding lithium capacity of graphite-like material with carbon element, and had excellent cycle performance.
Embodiment 4
Get the CoCl of 0.5mol/l 2Solution 100ml places flask, is the NaBH of 1mol/l then with 150ml concentration 4Solution joins in the flask; In this process, the solution in the flask is carried out magnetic agitation.After reaction finishes, stop stirring and make the suspension-turbid liquid layering.Supernatant liquor is removed; The lower sediment thing is taken out,, in eluate, drip AgNO with deionized water wash, suction filtration 3Solution no longer produces white precipitate.The sediment that above-mentioned suction filtration is crossed continues 500 ℃ of heating 1 hour down after 90 ℃ of following vacuumize, after the cooling boride.Through inducing the coupling plasma spectroscopy, consist of Co 1.00B 1.01O 0.48
The negative pole preparation method who with the boride is active matter is as follows: with above-mentioned synthetic boride, as the N-methyl pyrrolidone solution of the Kynoar of binding agent, mix as the Co powder of the conductive agent mass ratio with 80: 10: 10, be modulated into slurry, evenly be coated on the Copper Foil as the afflux utmost point, and oven dry.
The negative pole cutting for preparing is in blocks, and with commercial
Figure C20061008325400062
2300 barrier films, metal lithium sheet are assembled into Experimental cell, and electrolyte adopts 1M LiPF 6-EC/DMC (vol 1: 1).Experimental cell is after ageing in 24 hours, with 0.01mA/cm 2Current density carry out charge-discharge test, discharge cut-off voltage is 0.005V, the charging cut-ff voltage is 2V.Its first discharge capacity reach 426mAh/g, surpassed the theoretical embedding lithium capacity of graphite-like material with carbon element, and had excellent cycle performance.

Claims (7)

1. one kind is the lithium secondary battery of negative material with the metal boride, forms to comprise negative pole, positive pole, barrier film, electrolyte or polymer dielectric; Positive pole includes the transition metal oxide that contains lithium, or li-contained phosphate, or lithium metal; Separate by barrier film that has soaked electrolyte or polymer dielectric between positive pole and the negative pole; Positive electrode active material and negative electrode active material are coated in afflux respectively and extremely go up, and link to each other with the battery case two ends of mutually insulated by the afflux utmost point; It is characterized in that: negative pole is made up of metal boride, binding agent and conductive agent, and used negative active core-shell material is a metal boride.
2. described by claim 1 is the lithium secondary battery of negative material with the metal boride, it is characterized in that: the chemical composition of described metal boride is M aB bO cWherein M is selected from one or more among Co, Al, Zr, V, Cr, Ni, Fe, Ti, Cu, Zn, Nd, Mo, Ag, the Mg; 1≤a≤4,0.04≤b≤1,0≤c≤4; The structural form of metal boride is crystalline state or amorphous state.
By claim 1 or 2 described be the lithium secondary battery of negative material with the metal boride, it is characterized in that: solwution method, roasting method, ball-milling method, reducing process or the precipitation method are adopted in the preparation of described metal boride.
By claim 1 or 2 described be the lithium secondary battery of negative material with the metal boride, it is characterized in that: described binding agent is selected from one or more in Kynoar, polytetrafluoroethylene, polyacrylate, methylcellulose, polymethacrylates, polyvinyl alcohol, the vinylidene fluoride-hexafluoropropylene copolymer.
By claim 1 or 2 described be the lithium secondary battery of negative material with the metal boride, it is characterized in that: described conductive agent is selected from one or more in acetylene black, graphite, carbonaceous mesophase spherules, metal powder, the alloyed powder.
By claim 1 or 2 described be the lithium secondary battery of negative material with the metal boride, it is characterized in that: do not use conductive agent in the negative pole.
By claim 1 or 2 described be the lithium secondary battery of negative material with the metal boride, it is characterized in that: described negative current collector is selected from a kind of in wire netting, metal forming, carbon cloth, carbon paper, the nickel foam.
CNB200610083254XA 2006-06-01 2006-06-01 Lithium secondary cell using boride as negative polar material Expired - Fee Related CN100413139C (en)

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Publication number Priority date Publication date Assignee Title
CN105314643A (en) * 2014-07-28 2016-02-10 北京理工大学 Boride alkaline rechargeable battery negative electrode material and preparation method therefor
KR102323215B1 (en) * 2015-05-20 2021-11-08 삼성전자주식회사 Electrode active material, electrode and energy storage device including the same, and method for preparing the electrode active material
CN111244444A (en) * 2020-01-15 2020-06-05 上海电力大学 Borate lithium ion battery cathode material and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6395427B1 (en) * 1999-11-04 2002-05-28 Samsung Sdi Co., Ltd. Negative active material for rechargeable lithium battery and method of preparing same
US20040048157A1 (en) * 2002-09-11 2004-03-11 Neudecker Bernd J. Lithium vanadium oxide thin-film battery
CN1496588A (en) * 2001-03-06 2004-05-12 ������ѧ��ʽ���� Graphite material for negative pole of lithium secondary battery, method of manufacturing graphite material, and lithium secondary battery
US20040131940A1 (en) * 2001-05-15 2004-07-08 Takashi Suzuki Nonaqueous electrolytic secondary battery and method of producing anode material thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6395427B1 (en) * 1999-11-04 2002-05-28 Samsung Sdi Co., Ltd. Negative active material for rechargeable lithium battery and method of preparing same
CN1496588A (en) * 2001-03-06 2004-05-12 ������ѧ��ʽ���� Graphite material for negative pole of lithium secondary battery, method of manufacturing graphite material, and lithium secondary battery
US20040131940A1 (en) * 2001-05-15 2004-07-08 Takashi Suzuki Nonaqueous electrolytic secondary battery and method of producing anode material thereof
US20040048157A1 (en) * 2002-09-11 2004-03-11 Neudecker Bernd J. Lithium vanadium oxide thin-film battery

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