CN100433421C - 3V chargeable lithium ino battery and its production - Google Patents

3V chargeable lithium ino battery and its production Download PDF

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Publication number
CN100433421C
CN100433421C CNB2004100102942A CN200410010294A CN100433421C CN 100433421 C CN100433421 C CN 100433421C CN B2004100102942 A CNB2004100102942 A CN B2004100102942A CN 200410010294 A CN200410010294 A CN 200410010294A CN 100433421 C CN100433421 C CN 100433421C
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battery
lithium ion
ion battery
chargeable lithium
slurry
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CN1585169A (en
Inventor
李长杰
赵丽
杨书廷
李继刚
杨瑞
王书强
王慧
任英姿
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Henan Li-Power Supply Co., Ltd.
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ZHONGKE SCIENCE-TECHNOLOGY Co Ltd XINXIANG
HENAN JINLONG PRECISE COPPER PIPE 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
    • H01M4/58—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
    • 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
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • 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
    • 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
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The present invention discloses a 3V chargeable lithium ion battery and a producing method thereof, and relates to a battery. A technical problem needs to be solved so as to design a chargeable lithium ion battery with 3V voltage. Lithium ferrous phosphate is used as the anode material of the 3V chargeable lithium ion battery. The 3V chargeable lithium ion battery has the following producing processes: a slurry mixing process (1): mixing the solvent and the adhesive agent with anode active materials of the lithium ferrous phosphate; a slurry drawing process (2): coating the slurry materials on the surface of metallic foil; and heating and drying the slurry material to make the anode of the battery. The 3V chargeable lithium ion battery fills the gap of a 3V lithium ion battery, and can be used for the technical field of cameras, digital cameras, personal stereos, instruments, meters, electric toys, domestic electrical devices, etc.

Description

A kind of 3V rechargeable type lithium ion battery and manufacture craft thereof
Technical field:
The present invention relates to a kind of battery, particularly a kind of 3V rechargeable type lithium ion battery and manufacture craft thereof.
Background technology:
Along with the large-scale popularization of high-tech products such as all kinds of precision instrumentations, electric tool, electronic toy and home electronic appliance is used, people's active demand high energy, cheapness, environmental protection, safe, durable chemical power source (battery) product satisfy continuous demand.
At present, still generally use traditional disposable chemical power source (battery) (as dry cell, alkaline Mn cell) in these applications, such battery operated voltage is 1.5V/, generally is combined into different modes such as 3V, 6V, 9V when reality is used.But disposable battery exists to charge and carries out the defective that secondary uses, and cause resource significant wastage, actual use cost higher, and environmental issue (especially mercury pollution) is very outstanding.The disposable lithium cell operating voltage is 3.0V, but cost height, poor stability have limited it and promoted the use of.Secondary cell has plumbic acid, cadmium nickel, hydrogen nickel and lithium ion battery etc.Because the lead-acid battery operating voltage is 2V, NI-G, Ni-MH battery are 1.2V, traditional lithium ion battery voltage is 3.6V, all can't under the condition of work of n * 3V, use, and plumbic acid, ickel-cadmium cell environmental pollution problem are comparatively outstanding, hydrogen nickel and the restriction of lithium ion battery operating voltage can not substitute n * 1.5V series of products fully, and use can damage consuming device and cause environmental pollution by force.
Summary of the invention:
The technical issues that need to address of the present invention are a kind of 3V of having voltage of design and rechargeable type lithium ion battery.Another technical problem that the present invention need solve provides a kind of production technology of 3V rechargeable type lithium ion battery of suitable suitability for industrialized production.Technical scheme of the present invention is, a kind of 3V rechargeable type lithium ion battery, and it comprises positive pole, it is characterized in that: the ferrous lithium LiFe of anodal bad temper material selection modified phosphate 1-xM xPO 4, M=La, Nd, Pr, Gd or Ce, 0＜X＜1.Battery discharge platform 3.1-3.3V/ only exactly can satisfy 3V series electricity consumption system.Have high-energy-density, advantage such as price is low, security performance good, pollution-free, function admirable.Its cycle life surpasses more than 500 times, voltage compatibility is good, and can satisfy the instructions for use under n * 3V condition of work fully, can substitute disposable battery fully in above-mentioned application, fill up the blank of 3V lithium rechargeable battery, enlarged the application of lithium ion battery.
Description of drawings:
Fig. 1 is the battery charge curve, and Fig. 2 is the battery discharge curve, and Fig. 3 is the battery cycle life curve.
Making step is as follows:
One, the chief component of battery is: positive plate, negative plate, dividing plate, electrolyte, shell etc.
Two, manufacturing process is:
1, selects LiFePO 4 (LiFePO for use 4) or LiFe 1-xM xPO 4(M=La, Co, Ni, Mn, Cr, Cu, Nd, Pr, Gd, C, Mo, Ce) is as this cell positive material.
2, select for use carbon (C) as this cell negative electrode material.
3, select macromolecule polypropylene or polypropylene-polyethylene composite micro porous film dividing plate for use as this battery positive/negative plate.
4, select carbonate solvent+lithium salts (EC+DEC+DMC+LiPF for use 6, EC+EMC+DMC+LiPF 6, EC+EMC+DEC+LiPF 6) liquid state and or two kinds of forms of gel-type electrolyte as this battery electrolyte.
(1) it is stacked that the pond has two kinds of utmost point group structures (1) takeup types (2).
(2) the battery surface structure has square, cylindrical and aluminum-plastic composite membrane flexible package etc.
(3) the battery pack that forms by battery combination with n * 3V operating voltage.
Three, manufacture craft general introduction:
1 and the slurry
Mix with the positive and negative electrode active material respectively with solvent and bonding agent, after high-speed stirred is even, make the anode and cathode slurry of pulpous state.
2, slurry
The slurry of making is coated in the surface of metal forming equably, and the positive and negative electrode pole piece is made in the oven dry of heating respectively.
3, assembling and activation
Order by positive plate, barrier film, negative plate stacks, and through reeling or the technology of lamination is made Battery Pole Core, again through technical process such as inject electrolyte, seal, promptly finishes the assembling process of battery in the housing of packing into, makes the finished product battery.Battery charging and discharging equipment with special use discharges and recharges activation, test to the finished product battery.
4, combination
According to different instructions for uses, it can be combined as different voltage series-n * 3V.
Four, its operation principle is: during 3V rechargeable type lithium ion cell charging,
Anodal reaction: LiFePO 4→ Li 1-xFePO 4+ xLi ++ xe -
Negative reaction: C+xLi ++ xe -→ CLix
Battery overall reaction: LiFePO 4+ C → Li 1-xFePO 4+ CLix
The back reaction of above-mentioned reaction takes place during discharge.
Five, battery performance:
See battery charge characteristic curve, battery discharge characteristic curve and battery cycle life characteristic curve.
Six, this battery advantage:
This lithium ion battery is the system that the traditional secondary lithium ion battery further develops, and has the various feature performance benefits of traditional secondary lithium ion battery: as: energy density height, charge is outstanding, self-discharge rate is little, do not have memory effect etc.Compare 3V rechargeable type lithium ion battery LiFePO 4 (LiFePO with traditional lithium ion battery 4) replacement cobalt acid lithium (LiCoO 2), overcome cobalt acid lithium poor stability, cost an arm and a leg, and cobalt (Co) to the pollution problem of environment, this battery environmental protection, price is low, fail safe good, do not need complicated charge and discharge protecting route protection, raw material resources are abundant, cost of manufacture is low; And its operating voltage is 3.0V, and discharge platform is steady, one-tenth 3V capable of being combined, n * 3V systems such as 6V, 9V, and voltage compatibility is good, and suitable application area is extensive.
Seven, all kinds of battery performance parameter contrasts: see the battery performance parameter contrast table.
For clearer explanation the present invention, enumerate following example, but it there is not any restriction to the present invention.
Embodiment 1:
Get LiFePO 4 ((LiFePO 4)+graphite powder (C)+Kynoar (PVDF))=((70-98%): (0.1-16%): (1.8-15%)) g mixes 4h with an amount of potassium base pyrrolidines copper (NMP) of coughing up, and is coated on the aluminium foil, forms anode pole pieces through 120 ℃ of oven dry.
Negative pole is selected graphite (C)+conductive agent+SBR+CMC=(85-97.5%) for use: (0.2-2%): (1-10%): (1-10%) g and an amount of water mixing 4h, be coated on the matrix (Copper Foil), and form cathode pole piece through 110 ℃ of oven dry.
Positive plate cuts size (mm): 355 * 41 * 0.125
Negative plate cuts size (mm): 375 * 42 * 0.110
Barrier film cuts size (mm): 800 * 44 * 0.025
Both positive and negative polarity pole piece and membrane coil are packed into after forming utmost point group in 14500 (AA) type battery container, add electrolyte 2.6-3.5 (g)/only.
Through after discharging and recharging activation, seal and form 14500 (AA) battery.
After testing, when discharging with 1C, battery reversible capacity 570-620mAh, charging voltage 3.75-4.2V, discharge platform 3.1-3.3V/, final discharging voltage 2.5-2.75V/, cycle life reaches 600-700 time.
Embodiment 2:
Get LiFePO 4 ((LiFe 0.9La 0.07Mn 0.3PO 4)+graphite powder (C)+Kynoar (PVDF))=((70-98%): (0.1-16%): (1.8-15%)) g mixes 4h with an amount of potassium base pyrrolidines copper (NMP) of coughing up, and is coated on the aluminium foil, forms anode pole pieces through 120 ℃ of oven dry.
Negative pole is selected graphite (C)+conductive agent+SBR+CMC=(85-97.5%) for use: (0.2-2%): (1-10%): (1-10%) g and an amount of water mixing 4h, be coated on the matrix (Copper Foil), and form cathode pole piece through 110 ℃ of oven dry.
Positive plate cuts size (mm): 355 * 41 * 0.120
Negative plate cuts size (mm): 375 * 42 * 0.115
Barrier film cuts size (mm): 800 * 44 * 0.025
Both positive and negative polarity pole piece and membrane coil are packed into after forming utmost point group in 14500 (AA) type battery container, add electrolyte 2.6-3.5 (g)/only.
Through after discharging and recharging activation, seal and form 14500 (AA) battery.
After testing, when discharging with 1C, battery reversible capacity 620-670mAh, charging voltage 3.75-4.2V, discharge platform 3.1-3.3V/, final discharging voltage 2.5-2.75V/, cycle life reaches 700-900 time.
Embodiment 3:
Get LiFePO 4 ((LiFe 0.85Ce 0.15PO 4)+graphite powder (C)+Kynoar (PVDF))=((70-98%): (0.1-16%): (1.8-15%)) g mixes 4h with an amount of potassium base pyrrolidines copper (NMP) of coughing up, and is coated on the aluminium foil, forms anode pole pieces through 120 ℃ of oven dry.
Negative pole is selected graphite (C)+conductive agent+SBR+CMC=(85-97.5%) for use: (0.2-2%): (1-10%): (1-10%) g and an amount of water mixing 4h, be coated on the matrix (Copper Foil), and form cathode pole piece through 110 ℃ of oven dry.
Positive plate cuts size (mm): 290 * 41 * 0.125
Negative plate cuts size (mm): 330 * 42 * 0.11
Barrier film cuts size (mm): 610 * 44 * 0.025
Both positive and negative polarity pole piece and membrane coil are packed into after forming utmost point group in the 572247 square battery housings, add electrolyte 1.8-2.4 (g)/only.
Through after discharging and recharging activation, seal and form 572247 square batteries.
After testing, when discharging with 1C, battery reversible capacity 320-350mAh, charging voltage 3.75-4.2V, discharge platform 3.1-3.3V/, final discharging voltage 2.5-2.75V/, cycle life reaches 700～900 times.
Embodiment 4:
Get LiFePO 4 ((LiFe 0.95Pr 0.05PO 4)+graphite powder (C)+Kynoar (PVDF))=((70-98%): (0.1-16%): (1.8-15%)) g mixes 4h with an amount of potassium base pyrrolidines copper (NMP) of coughing up, and is coated on the aluminium foil, forms anode pole pieces through 120 ℃ of oven dry.
Negative pole is selected graphite (C)+conductive agent+SBR+CMC=(85-97.5%) for use: (0.2-2%): (1-10%): (1-10%) g and an amount of water mixing 4h, be coated on the matrix (Copper Foil), and form cathode pole piece through 110 ℃ of oven dry.
Positive plate cuts size (mm): 395 * 42 * 0.130
Negative plate cuts size (mm): 445 * 43 * 0.125
Barrier film cuts size (mm): 850 * 44 * 0.015～0.020
Both positive and negative polarity pole piece and membrane coil are packed into after forming utmost point group in the 063048 type battery container, add electrolyte 2.6-3.5 (g)/only.
Through after discharging and recharging activation, seal and form 063048 type battery.
After testing, when discharging with 1C, battery reversible capacity 760～790mAh, charging voltage 3.75-4.2V, discharge platform 3.2V/, final discharging voltage 2.5-2.75V/, cycle life reaches 550-750 time.
Embodiment 5:
Get embodiment 33 made on 572247 type batteries and carry out tandem compound and become the 9V battery, battery pack is of a size of 20 * 23 * 50mm.After testing, when discharging with 1C, battery reversible capacity 280-330mAh, charging voltage 11.0-12.0V/ group, discharge platform 9.3-9.9V/, final discharging voltage 7.5V/, cycle life reaches 700-800 time.The digital display universal instrument of packing into after this battery charge is interior surveys operating position, but continuous discharge 15-30 days.
Seven, all kinds of battery performance parameter contrasts:
The battery performance parameter contrast table
Figure C20041001029400061

Claims (1)

1. 3V rechargeable type lithium ion battery, it comprises positive pole, it is characterized in that: positive electrode active materials is selected the ferrous lithium LiFe of modified phosphate for use 1-xM xPO 4, M=La, Nd, Pr, Gd or Ce, 0＜X＜1.
CNB2004100102942A 2004-05-21 2004-05-21 3V chargeable lithium ino battery and its production Active CN100433421C (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100369314C (en) * 2005-08-08 2008-02-13 河南环宇集团有限公司 Preparation method for high rate phosphate lithium ion battery and battery prepared thereby

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1320976A (en) * 2000-04-25 2001-11-07 索尼株式会社 Positive electrode and non-aqueous electrolyte cell
JP2002117907A (en) * 2000-10-06 2002-04-19 Sony Corp Nonaqueous electrolyte secondary battery
CN1348230A (en) * 2000-10-06 2002-05-08 索尼株式会社 Nonaqueous electrolyte battery
WO2002083555A2 (en) * 2001-04-10 2002-10-24 Zentrum Für Sonnenenergie- Und Wasserstoff-Forschung Baden-Württemberg, Gemeinnützige Stiftung Binary, ternary and quaternary lithium phosphates, method for the production thereof and use of the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1320976A (en) * 2000-04-25 2001-11-07 索尼株式会社 Positive electrode and non-aqueous electrolyte cell
JP2002117907A (en) * 2000-10-06 2002-04-19 Sony Corp Nonaqueous electrolyte secondary battery
CN1348230A (en) * 2000-10-06 2002-05-08 索尼株式会社 Nonaqueous electrolyte battery
WO2002083555A2 (en) * 2001-04-10 2002-10-24 Zentrum Für Sonnenenergie- Und Wasserstoff-Forschung Baden-Württemberg, Gemeinnützige Stiftung Binary, ternary and quaternary lithium phosphates, method for the production thereof and use of the same

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