CN106450277A - Electrode system used in low-temperature rate type lithium ion battery - Google Patents
Electrode system used in low-temperature rate type lithium ion battery Download PDFInfo
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- CN106450277A CN106450277A CN201610933510.3A CN201610933510A CN106450277A CN 106450277 A CN106450277 A CN 106450277A CN 201610933510 A CN201610933510 A CN 201610933510A CN 106450277 A CN106450277 A CN 106450277A
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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
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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
- 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
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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
- H01M4/362—Composites
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/52—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
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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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- 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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Abstract
The invention discloses an electrode system used in a low-temperature rate type lithium ion battery. The electrode system used in the low-temperature rate type lithium ion battery comprises a positive electrode and a negative electrode, wherein the positive electrode contains an active substance, a binder and a conducting agent, and the negative electrode contains artificial graphite, hard carbon, a conducting agent, a binder and oxalic acid; the active substance is lithium cobalt oxide LiCoO2 or lithium nickel cobalt manganese oxide LiNixCoyMn(1-x-y)O2. The low-temperature rate type lithium ion battery provided with the electrode system has the excellent discharge performance in a low-temperature environment.
Description
Technical field
The present invention relates to lithium ion battery, in particular it relates to the electrode system in low-temperature rate lithium ion battery.
Background technology
Lithium ion battery because its energy density is big, voltage platform is high, cycle performance is excellent, be easy to carry and safety and environmental protection and
Receive much concern, be widely used in various product.With scientific and technological progress, the development of society, portable product is towards miniature
Change, intelligent, multifunction development, the increase of product use environment complexity is it is desirable to the battery as energy source has more
Good ambient adaptability.And cryogenic property (low temperature refers generally to less than -10 DEG C) is as a weight considering the battery context suitability
Want index, it appears particularly important.When heavy-current discharge uses at low ambient temperatures, battery polarization increases common batteries, and electric discharge is flat
Platform reduces, and prematurely reaches discharge voltage, leads to discharge capacity of the cell very few or directly can not put electricity.
Content of the invention
It is an object of the invention to provide the electrode system in a kind of low-temperature rate lithium ion battery, there is this electrode system
Low-temperature rate lithium ion battery can have excellent discharge performance at low ambient temperatures.
To achieve these goals, the invention provides a kind of electrode system in low-temperature rate lithium ion battery, bag
Include positive pole and negative pole；Positive pole contains active substance, binding agent and conductive agent, and negative pole contains Delanium, hard carbon, conductive agent, glues
Knot agent and oxalic acid；Wherein, active substance is lithium and cobalt oxides LiCoO2Or nickel cobalt manganese oxidate for lithium LiNixCoyMn1-x-yO2.
By technique scheme, the present invention passes through the synergism of each material in positive and negative electrode, and then makes there is this electricity
The low-temperature rate lithium ion battery of electrode systems has excellent discharge performance at low ambient temperatures, through detection show this lithium from
The concrete cryogenic property of sub- battery is as follows：In the environment of 25 DEG C, 15C multiplying power current discharge, discharge capacity reaches rated capacity
More than 90%；At -40 DEG C, with 3-5C multiplying power current discharge, discharge capacity reaches more than the 85% of rated capacity；When 25 DEG C,
0.5C charging/3C discharge cycles 1000 times, capability retention is more than 80%；Security performance is good, meet IEC62133 and
UN38.3 safety test requires.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, with following tool
Body embodiment is used for explaining the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is 15C rate discharge curves figure at 25 DEG C for the lithium ion battery A1 in detection example 1；
Fig. 2 is 3C, 5C rate discharge curves figure at -40 DEG C for the lithium ion battery A1 in detection example 1；
Fig. 3 is the discharge and recharge of lithium ion battery A1 0.5C charging/3C electric discharge at 25 DEG C at -40 DEG C in detection example 1
Cyclic curve figure.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that it is described herein concrete
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides the electrode system in a kind of low-temperature rate lithium ion battery, including positive pole and negative pole；Positive pole
Containing active substance, binding agent and conductive agent, negative pole contains Delanium, hard carbon, conductive agent, binding agent and oxalic acid；Wherein, live
Property material be lithium and cobalt oxides LiCoO2Or nickel cobalt manganese oxidate for lithium LiNixCoyMn1-x-yO2(x, y are positive number and x+y≤1).
In the positive pole of the present invention, the content of each material can select in wide scope, but so that has this
Electrode system in this low-temperature rate lithium ion battery of electrode system has more excellent cryogenic property it is preferable that with just
On the basis of the gross weight of the solidss in extremely, the content of active substance is 94-95 weight %, and the content of binding agent is 0.5-3 weight
Amount %, the content of conductive agent is 0.5-3 weight %.
In the negative pole of the present invention, the content of each material can select in wide scope, but so that has this
Electrode system in this low-temperature rate lithium ion battery of electrode system has more excellent cryogenic property, with consolidating in negative pole
On the basis of the gross weight of body thing, the content of Delanium is 67-81 weight %, and the content of hard carbon is 15-25 weight %, conductive agent
Content be 1-3 weight %, the content of binding agent is 2-5 weight %, and the content of oxalic acid is 0.1-0.4 weight %.
In the positive pole of the present invention, the particle diameter of active substance can select in wide scope, but so that has
Electrode system in this low-temperature rate lithium ion battery of this electrode system has more excellent cryogenic property it is preferable that living
The D of property material50For 4-8um.
In the positive pole of the present invention, active substance can be pure lithium and cobalt oxides LiCoO2Or nickel cobalt manganese oxidate for lithium
LiNixCoyMn1-x-yO2Or by surface-treated compound, in order to improve further, there is this electrode system
The cryogenic property of the electrode system in this low-temperature rate lithium ion battery it is preferable that the surface of active substance through overdoping or
Person's coating modification is processed.Wherein, the concrete mode of doping or coating modification process can be various, but so that mixes
Miscellaneous or cladding material can be with LiCoO2Or nickel cobalt manganese oxidate for lithium LiNixCoyMn1-x-yO2Preferably compatible, more preferably
Ground, adulterates or the process of coating modification process is：By mixing Mg2+、Al3+、Ga3+Deng the cation that quantivalence is little and stable
Strengthen the stability of positive electrode, or strengthen it in the high nano material of the electric conductivity such as Surface coating Graphene, CNT and lead
Electrically.
Hereinafter will be described the present invention by embodiment.
Embodiment 1
Rated capacity is the low-temperature rate lithium ion battery A1 of 5Ah：It is made up of positive pole, negative pole, barrier film and electrolyte.Its
In, positive pole contains (calculating by the percentage by weight of solidss)：98.2%LiCoO2(D50For 5.2um), 0.8% binding agent
PVDF, 1% conductive agent CNT；Negative pole contains (calculating by the percentage by weight of solidss)：74% Delanium, 20% hard carbon,
1.5% conductive agent KS-6,1.5% conductive agent SP, 3% binding agent PVDF, 0.25% oxalic acid；From polyethylene ceramic membrane be every
Film；From the low-temperature electrolyte containing vinylene carbonate, fluorine ethylene carbonate.
Embodiment 2
A2 in the low-temperature rate lithium ion battery for 5Ah for the rated capacity：It is made up of positive pole, negative pole, barrier film and electrolyte.
Wherein, positive pole contains (calculating by the percentage by weight of solidss)：96%LiCoO2(D50For 7.2um), 2% binding agent PVDF,
2% conductive agent CNT；Negative pole contains (calculating by the percentage by weight of solidss)：78% Delanium, 15% hard carbon, 3% conduction
Agent SP, 4% binding agent PVDF, 0.15% oxalic acid；It is barrier film from polyethylene ceramic membrane；From containing vinylene carbonate,
The low-temperature electrolyte of fluorine ethylene carbonate.
Embodiment 3
Method according to embodiment 1 carries out being obtained the low-temperature rate lithium ion battery A3 that rated capacity is 5Ah, and institute is different
, by the LiCoO in positive pole2It is changed to LiNi0.4Co0.1Mn0.5O2.
Embodiment 4
Method according to embodiment 1 carries out being obtained the low-temperature rate lithium ion battery A4 that rated capacity is 5Ah, and institute is different
, by the LiCoO in positive pole2It is changed to LiNi0.6Co0.2Mn0.2O2.
Embodiment 5
Method according to embodiment 1 carries out being obtained the low-temperature rate lithium ion battery A5 that rated capacity is 5Ah, and institute is different
, by the LiCoO in positive pole2It is changed to LiNi0.5Co0..2Mn0.3O2.
Embodiment 6
Method according to embodiment 1 carries out the electrode being obtained in the low-temperature rate lithium ion battery that rated capacity is 5Ah
System A6, except that, the LiCoO in positive pole2Have passed through doping treatment, the process of specific doping is：By mixing Mg2 +、Al3+And Ga3+Cation.
Embodiment 7
Method according to embodiment 1 carries out the electrode being obtained in the low-temperature rate lithium ion battery that rated capacity is 5Ah
System A7, except that, the LiCoO in positive pole2Have passed through coating modification to process, the process that specific coating modification is processed
For：In Surface coating Graphene and CNT.
Detection example 1
1) 15C multiplying power discharging situation at 25 DEG C for the A1 in detection low-temperature rate lithium ion battery, concrete outcome is shown in figure
1.
2) A1 3C, 5C multiplying power discharging situation at -40 DEG C in detection low-temperature rate lithium ion battery, concrete outcome is shown in figure
2 (curve of top is 3C rate discharge curves, and the curve of lower section is 5C rate discharge curves).
3) in detection low-temperature rate lithium ion battery, the charge and discharge cycles of 0.5C charging/3C electric discharge at 25 DEG C for the A1 are electric
Stream situation, concrete outcome is shown in Fig. 3.
By Fig. 1-3, in low-temperature rate lithium ion battery, the performance of A1 is as follows：In the environment of 25 DEG C, 15C times
Rate current discharge, discharge capacity reaches more than the 90% of rated capacity；At -40 DEG C, with 3-5C multiplying power current discharge, discharge capacity
Reach more than the 85% of rated capacity；When 25 DEG C, 0.5C charging/3C discharge cycles 1000 times, capability retention is more than 80%.
In the same manner, according to above-mentioned method, low-temperature rate lithium ion battery A2-A7 is detected；Wherein, the inspection of A2-A5
Survey result to be substantially consistent with the testing result of A1；The testing result of A6-A7 is better than the testing result of A1.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, multiple simple variant can be carried out to technical scheme, this
A little simple variant belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to various can
The compound mode of energy no longer separately illustrates.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as it is without prejudice to this
The thought of invention, it equally should be considered as content disclosed in this invention.
Claims (6)
1. the electrode system in a kind of low-temperature rate lithium ion battery is it is characterised in that include positive pole and negative pole；Described positive pole
Containing active substance, binding agent and conductive agent, described negative pole contains Delanium, hard carbon, conductive agent, binding agent and oxalic acid；Its
In, described active substance is lithium and cobalt oxides LiCoO2Or nickel cobalt manganese oxidate for lithium LiNixCoyMn1-x-yO2.
2. the electrode system in low-temperature rate lithium ion battery according to claim 1, wherein, with described positive pole
On the basis of the gross weight of solidss, the content of described active substance is 94-95 weight %, and the content of described binding agent is 0.5-3
Weight %, the content of described conductive agent is 0.5-3 weight %.
3. the electrode system in low-temperature rate lithium ion battery according to claim 1, wherein, with described negative pole
On the basis of the gross weight of solidss, the content of described Delanium is 67-81 weight %, and the content of described hard carbon is 15-25 weight
Amount %, the content of described conductive agent is 1-3 weight %, and the content of described binding agent is 2-5 weight %, and the content of described oxalic acid is
0.1-0.4 weight %.
4. the electrode system in the low-temperature rate lithium ion battery according to any one in claim 1-3, wherein, institute
State the D of active substance50For 4-8um.
5. the electrode system in low-temperature rate lithium ion battery according to claim 4, wherein, described active substance
Surface is processed through overdoping or coating modification.
6. the electrode system in low-temperature rate lithium ion battery according to claim 5, wherein, described doping or wrap
The process covering modification is：By mixing Mg2+、Al3+Or Ga3+Cation, or in Surface coating Graphene or CNT.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107093718A (en) * | 2017-04-18 | 2017-08-25 | 北京北方华创新能源锂电装备技术有限公司 | A kind of low temperature resistant extended-life lithium ion battery |
| CN109728269A (en) * | 2018-12-18 | 2019-05-07 | 南京理工大学 | The preparation method of graphene coated cobalt lithium aluminate electrode material |
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| CN109728269B (en) * | 2018-12-18 | 2022-02-15 | 南京理工大学 | Preparation method of graphene-coated cobalt lithium aluminate electrode material |
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Application publication date: 20170222 |