CN106450202A - Positive and negative electrode materials and electrode system of high-compaction high-capacity lithium ion battery - Google Patents

Positive and negative electrode materials and electrode system of high-compaction high-capacity lithium ion battery Download PDF

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Publication number
CN106450202A
CN106450202A CN201610934909.3A CN201610934909A CN106450202A CN 106450202 A CN106450202 A CN 106450202A CN 201610934909 A CN201610934909 A CN 201610934909A CN 106450202 A CN106450202 A CN 106450202A
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weight
lithium ion
content
binding agent
positive
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CN201610934909.3A
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Chinese (zh)
Inventor
沈晓彦
黄金健
王兴威
李玲俐
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JIANGSU NEW POWER BATTERY AND MATERIAL ENGINEERING TECHNOLOGY RESEARCH CENTRAL Co Ltd
JIANGSU HIGHSTAR BATTERY MANUFACTURING Co Ltd
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JIANGSU NEW POWER BATTERY AND MATERIAL ENGINEERING TECHNOLOGY RESEARCH CENTRAL Co Ltd
JIANGSU HIGHSTAR BATTERY MANUFACTURING Co Ltd
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Priority to CN201610934909.3A priority Critical patent/CN106450202A/en
Publication of CN106450202A publication Critical patent/CN106450202A/en
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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
    • H01M4/364—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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • 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
    • 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 & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses a positive and negative electrode materials and electrode system of a high-compaction high-capacity lithium ion battery. The positive electrode material contains active matter, an adhesive and a conductive agent. The active matter contains LiNi0.8Co0.15Al0.05O2(NCA) and lithium-cobalt oxide LiCoO2(LCO). The negative electrode material contains composite graphite, a conductive agent and an adhesive. Based on the total weight of solids in the negative electrode material, the content of the composite graphite is 92-97 wt%, the content of the conductive agent is 1-3 wt%, and the content of the adhesive is 2-5 wt%. The electrode system comprises a positive electrode and a negative electrode. The positive electrode is prepared from the positive electrode material, and the negative electrode is prepared from the negative electrode material. The lithium ion battery with the electrode system is excellent in compaction density and gram capacity.

Description

The positive and negative electrode material of high-pressure solid high-capacity lithium ion cell and electrode system
Technical field
The present invention relates to lithium ion battery, in particular it relates to the positive and negative electrode material of high-pressure solid high-capacity lithium ion cell with And electrode system.
Background technology
Lithium ion battery has the advantages that high energy density, high discharge platform, is widely used in 3C electronic product, electronic Instrument and energy-storage battery field.With the development of lithium battery technology, every profession and trade requires more and more higher, lithium to performance of lithium ion battery Ion battery products increasingly tend to developing to directions such as high power capacity, light weight, high rate performance and good cycle, especially high energy Metric density high-pressure solid direction.
High-energy-density, mainly compacted density and gram volume by improving material are realized.LiCoO2It is to make at present With most commonly used positive electrode although it has larger compacted density, but its own gram volume compared with NCM and NCA simultaneously Not high, generally improving its gram volume in the way of lifting charging/discharging voltage, but under high voltage material structure and unstable and Can be along with substantial amounts of side reaction under high voltage；For NCM, its compacted density is relatively low, although leading to its gram volume high, Volume energy density is not high.
Content of the invention
It is an object of the invention to provide a kind of positive and negative electrode material of high-pressure solid high-capacity lithium ion cell and electrode system System, the lithium ion battery containing this electrode system has excellent compacted density and gram volume.
To achieve these goals, the invention provides a kind of positive electrode of high-pressure solid high-capacity lithium ion cell, it is somebody's turn to do Pole material contains active material, binding agent and conductive agent；Wherein, active material contains nickel cobalt aluminium LiNi0.8Co0.15Al0.05O2 (NCA) with lithium and cobalt oxides LiCoO2(LCO).
Present invention also offers a kind of negative material of high-pressure solid high-capacity lithium ion cell, this negative material contains compound Graphite, conductive agent and binding agent；Wherein, on the basis of the gross weight of the solids in negative material, the content of composite graphite is 92-97 weight %, the content of conductive agent is 1-3 weight %, and the content of binding agent is 2-5 weight %.
Invention further provides this electrode systems of electrode system of a kind of high-pressure solid high-capacity lithium ion cell are just included Pole and negative pole；Positive pole is prepared from by upper positive electrode, and negative pole is prepared from by above-mentioned negative material.
By technique scheme, the present invention is by using LiCoO2Compacted density is high but gram volume is low, NCA material capacity (NCA compacted density is 3.5g/cm for the high but compacted density feature low compared with LCO3-3.55g/cm3, gram volume is 184mAh/g (1C), LCO compacted density is 3.9g/cm3-4.1g/cm3, gram volume is 146mAh/g (1C)), by the collaborative effect of LCO and NCA The high-pressure solid high-capacity lithium ion cell containing this electrode system should be made to have excellent compacted density and gram volume：- 20 At DEG C, with 0.2C multiplying power current discharge, discharge capacity reaches the 80% of rated capacity；At 25 DEG C, 1C charging/1C discharge cycles 500 times, more than 80%, security performance is good for capability retention.Wherein, after NCA mixing LCO, the compacting of the material of positive pressure pole is close Degree may be up to 3.7g/cm3；The 0.5C capacity energy of the battery providing with respect to the battery for pure NCA for the active material, the present invention Enough improve more than 5%.
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 specification, 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 detection example 1 intermediate ion battery A1, B1 1C rate discharge curves figure at -20 DEG C；
Fig. 2 is detection example 1 intermediate ion battery A1, B1 0.5C rate discharge curves figure at 25 DEG C；
Fig. 3 is the electric cyclic curve figure of detection example 1 intermediate ion battery A1, B1 1C charging/1C electric discharge at 25 DEG C.
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 a kind of positive electrode of high-pressure solid high-capacity lithium ion cell, this pole material contains active matter Matter, binding agent and conductive agent；Wherein, active material contains nickel cobalt aluminium LiNi0.8Co0.15Al0.05O2And lithium and cobalt oxides (NCA) LiCoO2(LCO).
In the present invention, in positive pole, the consumption of each material can select in wide scope, but in order that the height being obtained Compacting high-capacity lithium ion cell has more excellent compacted density and gram volume；Preferably, with the solids in positive electrode Gross weight on the basis of, the content of active material is 94-99 weight %, and the content of binding agent is 0.5-3 weight %, conductive agent Content is 0.5-3 weight %.
In the present invention, the weight ratio of NCA and LCO can select in wide scope, but in order that the high pressure being obtained Real high-capacity lithium ion cell has more excellent compacted density and gram volume；Preferably, the weight of NCA and LCO is than for 1：9- 9：1.
Present invention also offers a kind of negative material of high-pressure solid high-capacity lithium ion cell, this negative material contains compound Graphite, conductive agent and binding agent；Wherein, on the basis of the gross weight of the solids in negative material, the content of composite graphite is 92-97 weight %, the content of conductive agent is 1-3 weight %, and the content of binding agent is 2-5 weight %.
Invention further provides a kind of electrode system of high-pressure solid high-capacity lithium ion cell, this electrode systems is just included Pole and negative pole；Positive pole is prepared from by upper positive electrode, and negative pole is prepared from by above-mentioned negative material.
In the present invention, the concrete species of binding agent can select in wide scope, but in order that the high pressure being obtained Real high-capacity lithium ion cell has more excellent compacted density and gram volume；Preferably, the binding agent of positive pole is polyvinylidene fluoride Alkene (PVDF), the binding agent of negative pole is sodium carboxymethylcellulose (CMC) and/or butadiene-styrene rubber (SBR).
In the present invention, the concrete species of conductive agent can select in wide scope, but in order that the high-pressure solid being obtained High-capacity lithium ion cell has more excellent compacted density and gram volume；Preferably in described positive pole with negative pole, conductive agent For one or more of carbon black, electrically conductive graphite, acetylene black and CNT.
Hereinafter will be described the present invention by embodiment.
Embodiment 1
Rated capacity is the high-pressure solid high-capacity lithium ion cell A1 of 2.6Ah：By positive pole, negative pole, barrier film and electrolyte group Become.Wherein, positive pole contains (calculating by the percentage by weight of solids)：LiNi0.8Co0.15Al0.05O2(NCA) (71.3%), lithium Cobalt/cobalt oxide LiCoO2(25%), 2% binding agent PVDF, 0.7% conductive agent SP, 1% conductive agent Ketjen black；Negative pole contains (to be pressed The percentage by weight of solids calculates)：95.2% Delanium, 1% conductive agent SP, 1.5% binding agent CMC, 2.3% binding agent SBR；It is barrier film from polyethylene ceramic membrane；From the low-temperature electrolyte containing vinylene carbonate, fluorine ethylene carbonate.
Embodiment 2
Method according to embodiment 1 carries out high-pressure solid high-capacity lithium ion cell A2 is obtained, except that：NCA contains Measure as 10 weight %, the content of LCO is 86.3 weight %.
Embodiment 3
Method according to embodiment 1 carries out high-pressure solid high-capacity lithium ion cell A3 is obtained, except that：NCA contains Measure as 86.3 weight %, the content of LCO is 10 weight %.
Embodiment 4
Method according to embodiment 1 carries out high-pressure solid high-capacity lithium ion cell A4 is obtained, except that, positive pole contains (calculating by the percentage by weight of solids)：Active material (99%), 0.5% binding agent PVDF, 0.5% conductive agent SP.
Embodiment 5
Method according to embodiment 1 carries out high-pressure solid high-capacity lithium ion cell A5 is obtained, except that：Positive pole contains (calculating by the percentage by weight of solids)：Active material (94%), 3% binding agent PVDF, 1.5% conductive agent SP, 1.5% leads Electric agent Ketjen black.
Embodiment 6
Method according to embodiment 1 carries out high-pressure solid high-capacity lithium ion cell A6 is obtained, except that：Positive pole contains (calculating by the percentage by weight of solids)：Negative pole contains (calculating by the percentage by weight of solids)：92% Delanium, 3% conductive agent, 5% binding agent.
Embodiment 7
Method according to embodiment 1 carries out high-pressure solid high-capacity lithium ion cell A7 is obtained, except that：Positive pole contains (calculating by the percentage by weight of solids)：Negative pole contains (calculating by the percentage by weight of solids)：97% Delanium, 1% conductive agent, 2% binding agent.
Comparative example 1
Rated capacity is the lithium ion battery B1 of 2.6Ah：It is made up of positive pole, negative pole, barrier film and electrolyte.Wherein, positive pole Containing (calculating by the percentage by weight of solids)：LiNi0.8Co0.15Al0.05O2(NCA) (96.3%), 2% binding agent PVDF, 0.7% conductive agent SP, 1% conductive agent Ketjen black；Negative pole contains (calculating by the percentage by weight of solids)：95.2% composite stone Ink (the Jiangxi Zi Chen company trade mark is 8C, is mainly made up of carbon), 1% conductive agent SP, 1.5% binding agent CMC, 2.3% binding agent SBR；It is barrier film from polyethylene ceramic membrane；From the low-temperature electrolyte containing vinylene carbonate, fluorine ethylene carbonate.
Detection example 1
1) detect ion battery A1, B1 1C multiplying power discharging situation at -20 DEG C, concrete outcome is shown in Fig. 1.
2) detect ion battery A1, B1 0.5C multiplying power discharging situation at 25 DEG C, concrete outcome is shown in Fig. 2.
3) the charge and discharge cycles current conditions of 1C charging/1C electric discharge at 25 DEG C for detection ion battery A1, the B1, concrete knot Fruit sees Fig. 3.
4) detect the compacted density of positive pole in ion battery A1, B1.
In ion battery A1, the compacted density of positive pole is 3.7g/cm3, in ion battery B1, the compacted density of positive pole is 3.5g/cm3；By Fig. 1-3, the performance of high-pressure solid high-capacity lithium ion cell A1 is as follows：At -20 DEG C, with 0.2C times Rate current discharge, discharge capacity reaches the 80% of rated capacity；At 25 DEG C, 1C charging/1C discharge cycles 500 times, capacity is protected Holdup is more than 80%.A1 can improve more than 5% with respect to B1, the 0.5C capacity of battery
In the same manner, according to above-mentioned method, high-pressure solid high-capacity lithium ion cell A2-A7 is detected, testing result and A1 Testing result be substantially consistent.
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 combination of energy no longer separately illustrates.
Additionally, can also be combined 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 (7)

1. a kind of positive electrode of high-pressure solid high-capacity lithium ion cell is it is characterised in that described positive electrode contains active matter Matter, binding agent and conductive agent；Wherein, described active material contains nickel cobalt aluminium LiNi0.8Co0.15Al0.05O2(NCA) with lithium cobalt oxidation Thing LiCoO2(LCO).
2. positive electrode according to claim 1, wherein, with the gross weight of the solids in described positive electrode as base Standard, the content of described active material is 94-99 weight %, and the content of described binding agent is 0.5-3 weight %, described conductive agent Content is 0.5-3 weight %.
3. positive electrode according to claim 1 and 2, wherein, the weight of described NCA and LCO is than for 1：9-9：1.
4. a kind of negative material of high-pressure solid high-capacity lithium ion cell is it is characterised in that described negative material contains composite stone Ink, conductive agent and binding agent；Wherein, on the basis of the gross weight of the solids in described negative material, described composite graphite Content is 92-97 weight %, and the content of described conductive agent is 1-3 weight %, and the content of described binding agent is 2-5 weight %.
5. a kind of electrode system of high-pressure solid high-capacity lithium ion cell it is characterised in that described electrode system include positive pole and Negative pole；Described positive pole is prepared from by the described positive electrode of any one in claim 1-3, and described negative pole passes through right The described negative material in 4 is required to be prepared from.
6. electrode system according to claim 5, wherein, the binding agent of described positive pole is Kynoar, described negative pole Binding agent be sodium carboxymethylcellulose and/or butadiene-styrene rubber.
7. the electrode system according to claim 5 or 6, wherein, in described positive pole with negative pole, described conductive agent is carbon One or more of black, electrically conductive graphite, acetylene black and CNT.
CN201610934909.3A 2016-11-01 2016-11-01 Positive and negative electrode materials and electrode system of high-compaction high-capacity lithium ion battery Pending CN106450202A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101071859A (en) * 2007-06-07 2007-11-14 深圳市邦凯电子有限公司 Lithium cell anode active substance, anode dressing and its preparing method
CN104201374A (en) * 2014-09-11 2014-12-10 海宁美达瑞新材料科技有限公司 High-capacity lithium ion battery cathode material and preparation method thereof
CN104347880A (en) * 2014-10-14 2015-02-11 东莞新能源科技有限公司 Lithium ion battery capable of quick charging
CN104752671A (en) * 2015-03-09 2015-07-01 芜湖迈特电子科技有限公司 Quick charging back clip mobile battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101071859A (en) * 2007-06-07 2007-11-14 深圳市邦凯电子有限公司 Lithium cell anode active substance, anode dressing and its preparing method
CN104201374A (en) * 2014-09-11 2014-12-10 海宁美达瑞新材料科技有限公司 High-capacity lithium ion battery cathode material and preparation method thereof
CN104347880A (en) * 2014-10-14 2015-02-11 东莞新能源科技有限公司 Lithium ion battery capable of quick charging
CN104752671A (en) * 2015-03-09 2015-07-01 芜湖迈特电子科技有限公司 Quick charging back clip mobile battery

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王力臻 等: ""LiCoO2/LiNi0.8Co0.15Al0.05O2混合正极材料过充电行为研究"", 《电池工业》 *

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