CN104201376B - Li in controllable activation lithium-rich manganese-based anode material2MnO3The method of component - Google Patents

Li in controllable activation lithium-rich manganese-based anode material2MnO3The method of component Download PDF

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CN104201376B
CN104201376B CN201410483507.7A CN201410483507A CN104201376B CN 104201376 B CN104201376 B CN 104201376B CN 201410483507 A CN201410483507 A CN 201410483507A CN 104201376 B CN104201376 B CN 104201376B
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lithium
based anode
anode material
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mno
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CN104201376A (en
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刘昊
刘国标
刘焕明
梅军
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Chengdu Science and Technology Development Center of CAEP
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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
    • H01M4/48—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
    • 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
    • H01M4/36—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

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  • Chemical Kinetics & Catalysis (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
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  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses Li in a kind of controllable activation lithium-rich manganese-based anode material2MnO3The method of component, regulate and control Li by adjusting lithium-rich manganese-based anode material environment temperature residing during charge and discharge cycles2MnO3Be activated amount of the component under high potential during charge and discharge cycles, by different control methods, regulate and control Li in lithium-rich manganese-based anode material2MnO3Be activated amount of the component in charge and discharge cycles under more than or equal to 4.5V high potentials, so as to which the chemical property for optimization lithium-rich manganese-based anode material when charge and discharge cycles current potential is less than 4.4V provides new method.

Description

Li in controllable activation lithium-rich manganese-based anode material2MnO3The method of component
Technical field
The present invention relates to a kind of lithium ion anode material and electrochemical field, and in particular to a kind of controllable activation is lithium-rich manganese-based Li in positive electrode2MnO3The method of component.
Background technology
Up to the present, LiCoO2、LiMn2O4、LiNixCoyMnzO2、LiNi0.8Co0.15Al0.05O2And LiFePO4Deng just Pole material successful commercialization, however, being still hard to meet the fields such as intelligent grid, new-energy automobile to lithium ion battery just The requirement of pole material.Chemical formula is xLi2MnO3·(1-x)LiMO2The lithium-rich manganese-based anode material of (M=Ni, Co, Mn, Fe, Cr etc.) Material possesses specific capacity high, low in raw material price and the advantage such as relatively environment-friendly, is identified as most likely entering practical new Generation anode material for lithium-ion batteries.However, in order to obtain higher circulation volume, the discharge and recharge of lithium-rich manganese-based anode material follows Loop voltag is generally higher than 4.5V, however, high potential charge and discharge cycles easily cause cyclical stability difference and poor safety performance etc. to be Row problem.
The content of the invention
In view of this, it is an object of the invention to provide one kind solution to be currently in normal temperature and charge and discharge cycles upper voltage limit Li in lithium-rich manganese-based anode material is activated under the conditions of >=4.5V2MnO3Li can not be regulated and controled during component2MnO3Component activation amount is asked A kind of topic, there is provided Li in controllable activation lithium-rich anode material2MnO3The method of component.
Li in a kind of controllable activation lithium-rich manganese-based anode material of the present invention2MnO3The method of component, by adjusting rich lithium manganese Base anode material environment temperature residing during charge and discharge cycles regulates and controls Li2MnO3Component discharge and recharge under high potential follows The amount of being activated during ring；
Further, the ring residing during charge and discharge cycles by adjusting lithium-rich manganese-based anode material at low ambient temperatures Border temperature regulates and controls Li2MnO3The amount of being activated of component；
Further, pass through by the lithium ion battery of active material of lithium-rich manganese-based anode material in same environment temperature Discharge and recharge single cycle or multiple cyclic activation Li2MnO3Component；
Further, it is the lithium ion battery of active material in the environment temperature of different gradients using lithium-rich manganese-based anode material Pass through the multiple cyclic activation Li of discharge and recharge2MnO3Component；
Further, lithium ion battery using lithium-rich manganese-based anode material as active material is gradually increased or gradually reduced Pass through discharge and recharge single cycle or multiple cyclic activation Li in environment temperature2MnO3Component；
Further, the temperature of the low temperature environment is -40 DEG C~10 DEG C；
Further, the lithium-rich manganese-based anode material include the lithium-rich manganese-based anode material containing Ni, Co, Fe, Cr element with And containing Ca, Mg, Ti element doping or it is membrane wrapping modified after lithium-rich manganese-based anode material；
Further, the high potential is the voltage more than or equal to 4.5V.
Beneficial effects of the present invention：Li in the controllable activation lithium-rich manganese-based anode material of the present invention2MnO3The method of component, For Li in regulation and control lithium-rich manganese-based anode material2MnO3The activation amount of component provides a kind of effective new method, so as to have It is less than 4.4V chemical property in charge and discharge cycles upper voltage limit beneficial to optimization lithium-rich manganese-based anode material, is lithium-rich manganese-based Positive electrode enters a kind of practical new departure of offer.
Brief description of the drawings
It using lithium-rich manganese-based anode material is the lithium ion battery of active material under -20 DEG C of environment temperatures that Fig. 1, which is, is filled first Discharge cycles curve；
It using lithium-rich manganese-based anode material is the lithium ion battery of active material in the charge and discharge first of -20 DEG C of environment temperatures that Fig. 2, which is, Electric cyclic activation part Li2MnO3After component, the charge and discharge cycles curve under 25 DEG C of environment temperatures；
It using lithium-rich manganese-based anode material is the lithium ion battery of active material under -10 DEG C of environment temperatures that Fig. 3, which is, is filled first Discharge cycles curve；
It using lithium-rich manganese-based anode material is the lithium ion battery of active material in the charge and discharge first of -10 DEG C of environment temperatures that Fig. 4, which is, Electric cyclic activation part Li2MnO3After component, the charge and discharge cycles curve under 25 DEG C of environment temperatures；
It using lithium-rich manganese-based anode material is the lithium ion battery of active material under 0 DEG C of environment temperature that Fig. 5, which is, charge and discharge first Electric cyclic curve；
It using lithium-rich manganese-based anode material is the lithium ion battery of active material in 0 DEG C of environment temperature first charge-discharge that Fig. 6, which is, Cyclic activation part Li2MnO3After component, the charge and discharge cycles curve under 25 DEG C of environment temperatures；
It using lithium-rich manganese-based anode material is the lithium ion battery of active material under 10 DEG C of environment temperatures that Fig. 7, which is, is filled first Discharge cycles curve；
It using lithium-rich manganese-based anode material is the lithium ion battery of active material in 10 DEG C of environment temperature first charge-discharges that Fig. 8, which is, Cyclic activation part Li2MnO3After component, the charge and discharge cycles curve under 25 DEG C of environment temperatures；
It using lithium-rich manganese-based anode material is the lithium ion battery of active material under 25 DEG C of environment temperatures that Fig. 9, which is, is filled first Discharge cycles curve；
It using lithium-rich manganese-based anode material is the lithium ion battery of active material under 25 DEG C of environment temperatures that Figure 10, which is, secondary to fill Discharge cycles curve.
Embodiment
Li in a kind of controllable activation lithium-rich manganese-based anode material of the present embodiment2MnO3The method of component, by adjusting rich lithium Manganese-based anode material environment temperature residing during charge and discharge cycles regulates and controls Li2MnO3Component discharge and recharge under high potential The amount of being activated during circulation；It is anti-using active and electrochemistry of the temperature to lithium-rich manganese-based anode material during charge and discharge cycles The influence answered comes to regulating and controlling Li2MnO3Be activated amount of the component under high potential during charge and discharge cycles.
In the present embodiment, at low ambient temperatures by adjust lithium-rich manganese-based anode material during charge and discharge cycles it is residing Environment temperature regulate and control Li2MnO3The amount of being activated of component；By the lithium-ion electric using lithium-rich manganese-based anode material as active material Pond is placed in low temperature or ultra-low temperature surroundings, utilizes work of the lithium-rich manganese-based anode material in low temperature environment during charge and discharge cycles Property relatively low and electrochemical reaction relative delay, lithium ion battery carries out charge and discharge cycles even in the high potential more than 4.5V, Li in lithium-rich manganese-based anode material2MnO3Component is difficult to activate completely, so as to Li in lithium-rich manganese-based anode material2MnO3Component obtains Retain to part, and then can be by adjusting using lithium-rich manganese-based anode material as the environment residing for the lithium ion battery of active material Temperature regulates and controls Li2MnO3The amount of being activated of component.
It is the lithium ion battery of active material in same environment temperature using lithium-rich manganese-based anode material in the present embodiment Pass through discharge and recharge single cycle or multiple cyclic activation Li2MnO3Component.
In the present embodiment, using lithium-rich manganese-based anode material as active material lithium ion battery different gradients environment temperature Pass through the multiple cyclic activation Li of discharge and recharge in degree2MnO3Component.
In the present embodiment, the lithium ion battery using lithium-rich manganese-based anode material as active material is gradually increased or gradually dropped Pass through discharge and recharge single cycle or multiple cyclic activation Li in low environment temperature2MnO3Component.
In the present embodiment, preferably the temperature of low temperature environment is -40 DEG C~10 DEG C.
In the present embodiment, the lithium-rich manganese-based anode material includes the lithium-rich manganese-based anode material containing Ni, Co, Fe, Cr element Material and containing Ca, Mg, Ti element doping or it is membrane wrapping modified after lithium-rich manganese-based anode material.
In the present embodiment, the high potential is the voltage more than or equal to 4.6V.
Below by specific embodiment, the present invention is described further.
Embodiment one
With Li1.20Mn0.54Ni0.13Co0.13O2It is active material for lithium-rich manganese-based anode material, theoretical capacity 377mAh/ G, wherein belonging to Li2MnO3The capacity of component is 253mAh/g, belongs to LiMn1/3Ni1/3Co1/3O2The capacity of component is 124mAh/g.After the active material is assembled into button cell, place in high-low temperature chamber, it is -20 DEG C to set spin manifold temperature, is stood 4.0 hours, then, using current density as 30mA/g, voltage range be 2.0~4.8V charge and discharge cycles once, charging curve 4.5V platform is obvious, its corresponding capacity is 117mAh/g, Li1.20Mn0.54Ni0.13Co0.13O2Li in positive electrode2MnO3Component Activation amount is 46.2%.Then, the button cell after -20 DEG C of environment temperature initial activation is placed on temperature as 25 DEG C Environment in, stand 4.0 hours, then using current density as 30mA/g, be 2.0~4.8V charge and discharge cycles in voltage range, fill Electric curve 4.5V platforms are obvious, and its corresponding capacity is 143mAh/g, Li in the material2MnO3The activation amount of component is Li1.20Mn0.54Ni0.13Co0.13O2Middle Li2MnO3The 56.2% of component total amount.It can thus be appreciated that：It is -20 DEG C of bars by environment temperature Under part after first charge-discharge cyclic activation, Li in positive electrode2MnO3Constituent content is more than 56.2%.Then, in environment temperature For the battery after first charge-discharge cyclic activation under the conditions of -20 DEG C, it is placed in the environment that temperature is 25 DEG C, stands 4.0 hours, It is 3.0~4.4V charge and discharge cycles in voltage range using current density as 30mA/g, discharge capacity 143mAh/g, with 1500mA/g current density charge and discharge cycles, discharge capacity 56mAh/g.Using 150mA/g current densities in voltage range as 3.0 ~4.4V charge and discharge cycles 50 times, capability retention 93.9%.
Embodiment two
With Li1.20Mn0.54Ni0.13Co0.13O2It is active material for lithium-rich manganese-based anode material, theoretical capacity 377mAh/ G, wherein belonging to Li2MnO3The capacity of component is 253mAh/g, belongs to LiMn1/3Ni1/3Co1/3O2The capacity of component is 124mAh/g.After the active material is assembled into button cell, place in high-low temperature chamber, it is -10 DEG C to set spin manifold temperature, is stood 4.0 hours, then, using current density as 30mA/g, voltage range be 2.0~4.8V charge and discharge cycles once, charging curve 4.5V platforms are obvious, and its corresponding capacity is 149mAh/g, Li1.20Mn0.54Ni0.13Co0.13O2Li in positive electrode2MnO3Component Activation amount is 58.9%.Then, the button cell after -10 DEG C of environment temperature initial activation is placed on temperature as 25 DEG C Environment in, stand 4.0 hours, then using current density as 30mA/g, be 2.0~4.8V charge and discharge cycles in voltage range, fill Electric curve 4.5V platforms are obvious, and its corresponding capacity is 119mAh/g, Li in the material2MnO3The activation amount of component is Li1.20Mn0.54Ni0.13Co0.13O2Middle Li2MnO3The 47% of component total amount.It can thus be appreciated that：It is -10 DEG C of conditions by environment temperature After lower first charge-discharge cyclic activation, Li in positive electrode2MnO3Constituent content is more than 47%.Then, environment temperature for- Battery under the conditions of 10 DEG C after first charge-discharge cyclic activation, it is placed in the environment that temperature is 25 DEG C, stands 4.0 hours, with Current density is 30mA/g, is 3.0~4.4V charge and discharge cycles in voltage range, discharge capacity 170mAh/g.With 150mA/ G current densities are 3.0~4.4V charge and discharge cycles 50 times in voltage range, capability retention 90%.
Embodiment three
With Li1.20Mn0.54Ni0.13Co0.13O2It is active material for lithium-rich manganese-based anode material, theoretical capacity 377mAh/ G, wherein belonging to Li2MnO3The capacity of component is 253mAh/g, belongs to LiMn1/3Ni1/3Co1/3O2The capacity of component is 124mAh/g.After the active material is assembled into button cell, place in high-low temperature chamber, it is 0 DEG C to set spin manifold temperature, stands 4.0 Hour, then, using current density as 30mA/g, voltage range be 2.0~4.8V charge and discharge cycles once, charging curve 4.5V Platform is obvious, and its corresponding capacity is 180mAh/g, Li1.20Mn0.54Ni0.13Co0.13O2Li in positive electrode2MnO3The activation of component Measure as 71.1%.Then, the button cell after 0 DEG C of environment temperature initial activation is placed on the ring that temperature is 25 DEG C In border, 4.0 hours are stood, then is 2.0~4.8V charge and discharge cycles in voltage range using current density as 30mA/g, charging is bent Line 4.5V platforms are obvious, and its corresponding capacity is 85mAh/g, Li in the material2MnO3The activation amount of component is Li1.20Mn0.54Ni0.13Co0.13O2Middle Li2MnO3The 29.6% of component total amount.It can thus be appreciated that：It is 0 DEG C of condition by environment temperature After lower first charge-discharge cyclic activation, Li in positive electrode2MnO3Constituent content is 29.6~37.2%.Then, in environment temperature Spend for the battery after first charge-discharge cyclic activation under the conditions of 0 DEG C, be placed in the environment that temperature is 25 DEG C, stand 4.0 hours, It is 3.0~4.4V charge and discharge cycles in voltage range using current density as 30mA/g, discharge capacity 186mAh/g.With 150mA/g current densities are 3.0~4.4V charge and discharge cycles 50 times in voltage range, capability retention 83%.
Example IV
With Li1.20Mn0.54Ni0.13Co0.13O2It is active material for lithium-rich manganese-based anode material, theoretical capacity 377mAh/ G, wherein belonging to Li2MnO3The capacity of component is 253mAh/g, belongs to LiMn1/3Ni1/3Co1/3O2The capacity of component is 124mAh/g.After the active material is assembled into button cell, place in high-low temperature chamber, it is 10 DEG C to set spin manifold temperature, stands 4.0 Hour, then, using current density as 30mA/g, voltage range be 2.0~4.8V charge and discharge cycles once, charging curve 4.5V platforms are obvious, and its corresponding capacity is 196mAh/g, Li1.20Mn0.54Ni0.13Co0.13O2Li in positive electrode2MnO3Component Activation amount is 77.5%.Then, the button cell after 10 DEG C of environment temperature initial activation is placed on temperature as 25 DEG C Environment in, stand 4.0 hours, then using current density as 30mA/g, be 2.0~4.8V charge and discharge cycles in voltage range, fill Electric curve 4.5V platform unobvious.Then, the battery under the conditions of being 10 DEG C in environment temperature after first charge-discharge cyclic activation, It is in 25 DEG C of environment to be placed on temperature, stands 4.0 hours, using current density as 30mA/g, voltage range be 3.0~ 4.4V charge and discharge cycles, discharge capacity 183mAh/g.Using 150mA/g current densities in voltage range as 3.0~4.4V charge and discharges Electricity circulation 50 times, capability retention 90.5%.
Embodiment five
With Li1.20Mn0.54Ni0.13Co0.13O2It is active material for lithium-rich manganese-based anode material, theoretical capacity 377mAh/ G, wherein belonging to Li2MnO3The capacity of component is 253mAh/g, belongs to LiMn1/3Ni1/3Co1/3O2The capacity of component is 124mAh/g.After the active material is assembled into button cell, in the environment that room temperature is 25 DEG C, using current density as 30mA/g, It is 2.0~4.8V charge and discharge cycles in voltage range, charging curve 4.5V platforms are obvious, and its corresponding capacity is 218mAh/g, Li1.20Mn0.54Ni0.13Co0.13O2Li in positive electrode2MnO3The activation amount of component is 86%.Recharging circulates, charging curve 4.5V platform unobvious.Battery under the conditions of being 25 DEG C in environment temperature after first charge-discharge cyclic activation, using current density as 30mA/g, it is 3.0~4.4V charge and discharge cycles in voltage range, discharge capacity 178mAh/g, with 150 mA/g current densities It is 3.0~4.4V charge and discharge cycles 50 times in voltage range, capability retention 91.3%.By contrast, filled without high potential The battery of discharge cycles activation, is 3.0~4.4V charge and discharge cycles in voltage range using current density as 30mA/g, and electric discharge is held Measure as 85mAh/g, using 150mA/g current densities in voltage range as 3.0~4.4V charge and discharge cycles 50 times, capability retention is 95.1%.
Finally illustrate, the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to compared with The present invention is described in detail good embodiment, it will be understood by those within the art that, can be to the skill of the present invention Art scheme is modified or equivalent substitution, and without departing from the objective and scope of technical solution of the present invention, it all should cover at this Among the right of invention.

Claims (8)

  1. A kind of 1. Li in controllable activation lithium-rich manganese-based anode material2MnO3The method of component, it is characterised in that：By adjusting rich lithium Manganese-based anode material environment temperature residing during charge and discharge cycles regulates and controls Li2MnO3Component discharge and recharge under high potential The amount of being activated during circulation.
  2. 2. Li in controllable activation lithium-rich manganese-based anode material according to claim 12MnO3The method of component, its feature exist In：Regulated and controled at low ambient temperatures by adjusting lithium-rich manganese-based anode material environment temperature residing during charge and discharge cycles Li2MnO3The amount of being activated of component.
  3. 3. Li in controllable activation lithium-rich manganese-based anode material according to claim 1 or 22MnO3The method of component, its feature It is：Lithium ion battery using lithium-rich manganese-based anode material as active material passes through discharge and recharge single in same environment temperature Circulation or repeatedly cyclic activation Li2MnO3Component.
  4. 4. Li in controllable activation lithium-rich manganese-based anode material according to claim 1 or 22MnO3The method of component, its feature It is：Pass through discharge and recharge in the environment temperature of different gradients by the lithium ion battery of active material of lithium-rich manganese-based anode material Multiple cyclic activation Li2MnO3Component.
  5. 5. Li in controllable activation lithium-rich manganese-based anode material according to claim 1 or 22MnO3The method of component, its feature It is：Lithium ion battery using lithium-rich manganese-based anode material as active material be gradually increased or the environment temperature that gradually reduces in Pass through discharge and recharge single cycle or multiple cyclic activation Li2MnO3Component.
  6. 6. Li in controllable activation lithium-rich manganese-based anode material according to claim 22MnO3The method of component, its feature exist In：The temperature of the low temperature environment is -40 DEG C~10 DEG C.
  7. 7. Li in controllable activation lithium-rich manganese-based anode material according to claim 1 or 22MnO3The method of component, its feature It is：The lithium-rich manganese-based anode material include lithium-rich manganese-based anode material containing Ni, Co, Fe, Cr element and containing Ca, Mg, Ti element dopings or it is membrane wrapping modified after lithium-rich manganese-based anode material.
  8. 8. Li in controllable activation lithium-rich manganese-based anode material according to claim 1 or 22MnO3The method of component, its feature It is：The high potential is the voltage more than or equal to 4.5V.
CN201410483507.7A 2014-09-19 2014-09-19 Li in controllable activation lithium-rich manganese-based anode material2MnO3The method of component Active CN104201376B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101425603A (en) * 2007-09-28 2009-05-06 三洋电机株式会社 Alkaline storage battery system
CN103560266A (en) * 2013-11-07 2014-02-05 天津市捷威动力工业有限公司 Long-service-life lithium ion battery and manufacture method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07296850A (en) * 1994-04-28 1995-11-10 Matsushita Electric Ind Co Ltd Nonaqueous electrolyte lithium secondary battery

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101425603A (en) * 2007-09-28 2009-05-06 三洋电机株式会社 Alkaline storage battery system
CN103560266A (en) * 2013-11-07 2014-02-05 天津市捷威动力工业有限公司 Long-service-life lithium ion battery and manufacture method thereof

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