CN103606701A - Lithium ion secondary battery - Google Patents

Lithium ion secondary battery Download PDF

Info

Publication number
CN103606701A
CN103606701A CN201310577371.1A CN201310577371A CN103606701A CN 103606701 A CN103606701 A CN 103606701A CN 201310577371 A CN201310577371 A CN 201310577371A CN 103606701 A CN103606701 A CN 103606701A
Authority
CN
China
Prior art keywords
rechargeable battery
mixing
lithium rechargeable
battery according
active material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201310577371.1A
Other languages
Chinese (zh)
Other versions
CN103606701B (en
Inventor
陈璇
钱国珠
沈春平
黄满湘
秦丽
苏乐乐
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JIANGSU TENPOWER LITHIUM CO Ltd
Original Assignee
JIANGSU TENPOWER LITHIUM CO Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JIANGSU TENPOWER LITHIUM CO Ltd filed Critical JIANGSU TENPOWER LITHIUM CO Ltd
Priority to CN201310577371.1A priority Critical patent/CN103606701B/en
Publication of CN103606701A publication Critical patent/CN103606701A/en
Application granted granted Critical
Publication of CN103606701B publication Critical patent/CN103606701B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/624—Electric conductive fillers
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/42—Alloys based on zinc
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a lithium ion secondary battery. The lithium ion secondary battery comprises a positive pole piece, a negative pole piece, and a diaphragm and electrolyte arranged between the positive pole piece and the negative pole piece; a negative pole comprises a current collector and a discontinuous layer; the discontinuous layer comprises silicon and an active material I; a positive pole comprises a conductive base body, a conductive agent, an anode active material and a bonding agent; the conductive agent comprises a modified multi-wall carbon nano tube and a conductive agent I. According to the lithium ion secondary battery, the mass specific capacity of the lithium ion battery is improved and the cycling performance of the battery is not reduced.

Description

A kind of lithium rechargeable battery
Technical field
The present invention relates to battery, be specifically related to a kind of lithium rechargeable battery.
Background technology
Lithium ion battery is since commercialization is promoted, with its high-energy-density, high working voltage, have extended cycle life, memory-less effect, environmental protection and the large I of size shape according to the actual requirements the plurality of advantages such as flexible design be widely used as the power supply of various walkie electronic apparatus, the application that these are wide and various actual demand have greatly promoted the development of lithium ion battery.For the positive pole of lithium ion battery, current lithium ion battery, after meet improving multiplying power discharging property, can be paid the specific discharge capacity that can reduce battery mostly, and the cost that also decreases of cycle performance.Negative pole for lithium ion battery, in recent years, negative pole using silicon as lithium ion battery has carried out extensively and research meticulously, in charge and discharge process, lithium ion can take off embedding in silicon, when lithium ion is inserted in silicon, can form alloy with silicon, this silicium cathode material has high specific capacity, can reach 4200mAh/g in theory.
Summary of the invention
The object of the invention is the defect for above-mentioned prior art, a kind of lithium rechargeable battery is provided, when having the multiplying power discharging property of raising, the cyclicity of lithium ion battery is good, the advantage that specific discharge capacity is high.
Object of the present invention can be achieved through the following technical solutions:
A kind of lithium rechargeable battery, comprise positive plate, negative plate and be placed in barrier film and the electrolyte between positive and negative plate, described negative pole comprises collector body and discontinuity layer, described discontinuity layer comprises silicon and active material I, described positive pole comprises conducting base, conductive agent, positive active material and adhesive, and described conductive agent comprises modified multiwalled carbon nanotube and conductive agent I.
The making of described negative pole comprises the following steps:
A, silicon is mixed with 1:1～3 with active material I, obtain negative active core-shell material;
B, negative active core-shell material, adhesive I and water are mixed to obtain to slurry, the slurry obtaining is coated on collector body, carries out dry at 50～80 ℃, be 12～24 hours drying time, carry out the calendering that pressure is 1.5～4 MPas, the calendering time is 1～3 second again;
C, under inert atmosphere of nitrogen or the vacuum environment below 0.2 handkerchief, the negative pole after calendering is carried out to the sintering of 200～650 ℃, sintering time is 36～60 hours.
Described active material I is one or more mixing of titanium, iron, zinc, aluminium, nickel and copper, and described adhesive I is one or more mixing of polyvinyl alcohol, methyl fiber rope, hydroxy propyl cellulose and methylol fiber.
Described discontinuity layer, is loose structure, porosity for you 12～48%, with respect to the negative active core-shell material of 100 weight portions, the consumption of described adhesive is 5～20 weight portions, the weight of water is 100～180 weight portions.
The making of described many walls of modification nanotube comprises the following steps:
A, at 500～900 ℃, under the vacuum condition of 50～320 handkerchiefs or the protection of inert gas, the alkali that is 1～6:1 by weight ratio and many walls nanotube raw material haptoreaction 1～3 hour;
B, the catalytic product of gained is filtered and washed with water.
Described inert gas is nitrogen or argon gas, described alkali is one or more mixing of NaOH, KOH and LiOH, and the average caliber of described multi-wall carbon nano-tube structure is 30～75 nanometers, and length is 2～6 microns, the average caliber of described modified multiwalled carbon nanotube is 30～75 nanometers, and length is 1～5 micron.
Described conductive agent I is carbon black, graphite, acetylene black, carbon fiber, one or more mixing of copper powder, aluminium powder, zinc powder and iron powder.
Described conducting base is one or more mixing of aluminium, copper, nickel-plated steel or nickel, positive active material is one or more mixing of LiFePO 4, nickel hydroxide and phosphoric acid vanadium lithium, and described adhesive is one or more mixing in polytetrafluoroethylene, butadiene-styrene rubber, carboxymethyl cellulose, sodium carboxymethylcellulose, hydroxypropyl methylcellulose and POLYPROPYLENE GLYCOL.
Beneficial effect of the present invention: the present invention adopts silicium cathode material, improved battery specific capacity, and in the time of can avoiding de-embedding, negative pole change in volume causes the shortcoming that the cycle performance of lithium ion battery declines, and the positive pole that the present invention makes, improve the specific discharge capacity of lithium ion battery, and can not reduce the cyclicity of battery.
Embodiment
Below by embodiment, the present invention is described in detail.
For negative pole, by following steps, make:
The first step, the raw copper of the raw silicon of 100 weight portions and 200 weight portions is joined in the ball grinder of ball mill, wherein the weight of ball milling and the weight ratio of raw material are 12:1, ball grinder sealing is deflated and is filled with nitrogen, carry out ball milling 30 hours, obtain negative active core-shell material;
Second step, by the negative active core-shell material of 100 grams and 10 grams of polyvinyl alcohol, add in 150 grams of water, then in de-airing mixer, stir to form, the slurry of homogeneous.Slurry is all coated on the Copper Foil of 1 μ m, at 70 ℃, is dried 15 hours, dry pole piece is rolled 3 seconds under the pressure of 2 MPas;
The 3rd step, the negative pole of calendering is cut into required form, then, under the protection of nitrogen, at the environment of 400 ℃, carries out the sintering of 50 hours.Obtain the through-hole rate of discontinuous layer between 12%～48%.
For positive pole, first get LiOH36 gram, V 2o 590 grams, (NH 4) 2hPO 4300 grams of 200 grams, glucose, ethanol 50ml, is placed on mixing in high energy vibrations ball mill grinding jar ball milling 6 hours, again that batch mixing is dry rear with the moulding of roll-in Bigpian, it is 1 μ m that compressing tablet becomes thickness,, then sheet batch mixing is put into alumina crucible, and in crucible the active carbon of 30 grams of landfills, again crucible is heated to 10min in the microwave oven of 600 watts, product is become to the particle below 400 with air-flow crushing after being cooled to room temperature, get final product to obtain positive active material.
Getting 30 grams of NaOH is 30 nanometers with average caliber, length is that 10 grams of multi-walled carbon nano-tubes raw materials of 2 μ m mix, under the condition of nitrogen gas of 800 ℃, react two hours, then the atmosphere of nitrogen drops to room temperature, till more reacted modified multiwalled carbon nanotube being washed with water to washing lotion and becoming neutrality, both obtained modified multiwalled carbon nanotube.
By 100 restraints standby positive active material and 3 grams of butadiene-styrene rubber, 2.5 grams of modified multiwalled carbon nanotubes, 0.5 gram of average diameter is the flake graphite of 3 μ m, and 50 grams of deionized waters mix, with ultrasonic oscillation 40min, make suspension and through ultrasonic dispersion, mixture being ground in mortar to 100min and make pasty slurry, is on the Copper Foil of 20 μ m to thickness by slurry on foot, oven dry, roll extrusion at 160 ℃, cuts and obtains positive pole.
More than show and described basic principle of the present invention and principal character and advantage of the present invention.The technology people of the industry should understand; the present invention is not restricted to the described embodiments; that in above-described embodiment and specification, describes just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.

Claims (8)

1. a lithium rechargeable battery, comprise positive plate, negative plate and be placed in barrier film and the electrolyte between positive and negative plate, it is characterized in that: described negative pole comprises collector body and discontinuity layer, described discontinuity layer comprises silicon and active material I, described positive pole comprises conducting base, conductive agent, positive active material and adhesive, and described conductive agent comprises modified multiwalled carbon nanotube and conductive agent I.
2. a kind of lithium rechargeable battery according to claim 1, is characterized in that, the making of described negative pole comprises the following steps:
A, silicon is mixed with 1:1～3 with active material I, obtain negative active core-shell material;
B, negative active core-shell material, adhesive I and water are mixed to obtain to slurry, the slurry obtaining is coated on collector body, carries out dry at 50～80 ℃, be 12～24 hours drying time, carry out the calendering that pressure is 1.5～4 MPas, the calendering time is 1～3 second again;
C, under inert atmosphere of nitrogen or the vacuum environment below 0.2 handkerchief, the negative pole after calendering is carried out to the sintering of 200～650 ℃, sintering time is 36～60 hours.
3. a kind of lithium rechargeable battery according to claim 2, it is characterized in that: described active material I is one or more mixing of titanium, iron, zinc, aluminium, nickel and copper, and described adhesive I is one or more mixing of polyvinyl alcohol, methyl fiber rope, hydroxy propyl cellulose and methylol fiber.
4. a kind of lithium rechargeable battery according to claim 3, it is characterized in that: described discontinuity layer, for loose structure, porosity for you 12～48%, negative active core-shell material with respect to 100 weight portions, the consumption of described adhesive is 5～20 weight portions, and the weight of water is 100～180 weight portions.
5. a kind of lithium rechargeable battery according to claim 1, is characterized in that, the making of described many walls of modification nanotube comprises the following steps:
A, at 500～900 ℃, under the vacuum condition of 50～320 handkerchiefs or the protection of inert gas, the alkali that is 1～6:1 by weight ratio and many walls nanotube raw material haptoreaction 1～3 hour;
B, the catalytic product of gained is filtered and washed with water.
6. a kind of lithium rechargeable battery according to claim 5, it is characterized in that: described inert gas is nitrogen or argon gas, described alkali is one or more mixing of NaOH, KOH and LiOH, the average caliber of described multi-wall carbon nano-tube structure is 30～75 nanometers, length is 2～6 microns, the average caliber of described modified multiwalled carbon nanotube is 30～75 nanometers, and length is 1～5 micron.
7. a kind of lithium rechargeable battery according to claim 5, is characterized in that: described conductive agent I is carbon black, graphite, acetylene black, carbon fiber, one or more mixing of copper powder, aluminium powder, zinc powder and iron powder.
8. a kind of lithium rechargeable battery according to claim 1, it is characterized in that: described conducting base is one or more mixing of aluminium, copper, nickel-plated steel or nickel, positive active material is one or more mixing of LiFePO 4, nickel hydroxide and phosphoric acid vanadium lithium, and described adhesive is one or more mixing in polytetrafluoroethylene, butadiene-styrene rubber, carboxymethyl cellulose, sodium carboxymethylcellulose, hydroxypropyl methylcellulose and POLYPROPYLENE GLYCOL.
CN201310577371.1A 2013-11-15 2013-11-15 A kind of lithium rechargeable battery Active CN103606701B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310577371.1A CN103606701B (en) 2013-11-15 2013-11-15 A kind of lithium rechargeable battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310577371.1A CN103606701B (en) 2013-11-15 2013-11-15 A kind of lithium rechargeable battery

Publications (2)

Publication Number Publication Date
CN103606701A true CN103606701A (en) 2014-02-26
CN103606701B CN103606701B (en) 2016-01-20

Family

ID=50124914

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310577371.1A Active CN103606701B (en) 2013-11-15 2013-11-15 A kind of lithium rechargeable battery

Country Status (1)

Country Link
CN (1) CN103606701B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109546152A (en) * 2018-11-13 2019-03-29 南昌大学 A kind of solid lithium battery electrode material and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101420022A (en) * 2007-10-26 2009-04-29 比亚迪股份有限公司 Positive pole of lithium ionic cell
CN101436656A (en) * 2007-11-16 2009-05-20 比亚迪股份有限公司 Lithium ion battery cathode and preparation method thereof and lithium ion battery

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101420022A (en) * 2007-10-26 2009-04-29 比亚迪股份有限公司 Positive pole of lithium ionic cell
CN101436656A (en) * 2007-11-16 2009-05-20 比亚迪股份有限公司 Lithium ion battery cathode and preparation method thereof and lithium ion battery

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109546152A (en) * 2018-11-13 2019-03-29 南昌大学 A kind of solid lithium battery electrode material and preparation method thereof

Also Published As

Publication number Publication date
CN103606701B (en) 2016-01-20

Similar Documents

Publication Publication Date Title
Zhao et al. GO-graphene ink-derived hierarchical 3D-graphene architecture supported Fe3O4 nanodots as high-performance electrodes for lithium/sodium storage and supercapacitors
CN106654177B (en) Method for preparing battery capacitor composite electrode by dry method
CN105374991B (en) Lithium metal-skeleton carbon composite material and preparation method, cathode and secondary cell
Jiang et al. A sustainable route from fly ash to silicon nanorods for high performance lithium ion batteries
Chen et al. Graphene quantum dots modified nanoporous SiAl composite as an advanced anode for lithium storage
Idris et al. Effects of polypyrrole on the performance of nickel oxide anode materials for rechargeable lithium-ion batteries
CN111326715B (en) Battery positive electrode material and preparation method and application thereof
Jin et al. Pomegranate-like Li3VO4/3D graphene networks nanocomposite as lithium ion battery anode with long cycle life and high-rate capability
Zhang et al. A novel carbon nanotubes@ porous carbon/sulfur composite as efficient electrode material for high-performance lithium-sulfur battery
Wang et al. Cobalt phosphide nanoparticles grown on Ti3C2 nanosheet for enhanced lithium ions storage performances
Yao et al. Binder-free freestanding flexible Si nanoparticle–multi-walled carbon nanotube composite paper anodes for high energy Li-ion batteries
WO2023173772A1 (en) Preparation method for and use of hard carbon negative electrode material
Li et al. Hierarchical MnMoO4@ nitrogen-doped carbon core-shell microspheres for lithium/potassium-ion batteries
EP3913706A1 (en) Pre-lithiated negative electrode and preparation method therefor, and lithium ion battery and supercapacitor having pre-lithiated negative electrode
CN107887579B (en) Surface-modified polyanionic positive electrode material for lithium ion battery and preparation method thereof
Li et al. A novel Fe3O4/buckypaper composite as free-standing anode for lithium-ion battery
Zhang et al. Soft fully-printed rGO/Fe2O3-based supercapacitors for wearable electronics
Liao et al. Fabrication of SiOx-G/PAA-PANi/Graphene composite with special cross-doped conductive hydrogels as anode materials for lithium ion batteries
Wei et al. One-dimensional core-shell composite of AgNWs@ Si@ GO for high-specific capacity and high-safety anode materials of lithium-ion batteries
CN111697217A (en) Preparation method of silicon/graphite composite cathode of lithium ion battery
CN105047917A (en) Preparation method of lithium iron phosphate battery cathode material
CN113725013A (en) Preparation method of current collector-free electrode and application of current collector-free electrode in super capacitor
CN110707290B (en) Preparation method of flexible lithium ion battery negative electrode with sandwich-like structure
CN108630917A (en) Si @ C @ fibrous carbon @ C composite material and preparation method and application thereof
CN103606701B (en) A kind of lithium rechargeable battery

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant