CN113725411A - Anode material suitable for low-temperature environment and lithium ion battery - Google Patents

Anode material suitable for low-temperature environment and lithium ion battery Download PDF

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CN113725411A
CN113725411A CN202110989016.XA CN202110989016A CN113725411A CN 113725411 A CN113725411 A CN 113725411A CN 202110989016 A CN202110989016 A CN 202110989016A CN 113725411 A CN113725411 A CN 113725411A
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low
temperature environment
positive electrode
lithium ion
ion battery
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冯昂
卢孟萍
王忠华
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Changzhou Gaotai Information Technology 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
    • H01M4/362—Composites
    • 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
    • H01M4/58—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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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 a cathode material suitable for a low-temperature environment, which comprises the following substances in percentage by mass: 87% to 97% of lithium iron phosphate; 1% to 8% metal oxide; 1% to 3% of a positive electrode conductive agent; 1% to 3% binder; the invention also discloses a lithium ion battery which is made of the anode material and is suitable for low-temperature environment; according to the invention, by adding uniformly distributed metal oxide to the lithium iron phosphate, the electric contact between the lithium iron phosphate and a current collector is improved, the contact resistance is reduced, the electrode polarization of the anode is reduced, and the conductivity at low temperature is improved; the lithium ion battery obtained by the invention effectively reduces the internal impedance in a low-temperature environment, improves the charge and discharge efficiency of the battery, and prolongs the cycle life.

Description

Anode material suitable for low-temperature environment and lithium ion battery
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a cathode material suitable for a low-temperature environment, a lithium ion battery and a preparation method thereof.
Background
China is wide in territory and large in climate difference, so that the electric automobile faces severe tests of different climate environments in the use process. Particularly, in the aspect of temperature, the temperature of cold winter in the north is often reduced to-30 ℃, and the temperature has obvious influence on the performance, the service life, the safety and the like of the lithium ion battery.
LiFePO4The structure belongs to an orthorhombic system, is an olivine structure material, has the advantages of rich raw materials, low price, high specific capacity, high working voltage, stable structure, good cycle performance, environmental friendliness, safety and the like, and is considered as an ideal anode material of a power type lithium ion battery. However, the material has the defects of poor conductivity, low diffusion speed of lithium ions in the electrode material and unsatisfactory performance under high and low temperature conditions.
Lithium iron phosphate is a positive electrode material with high safety performance and long cycle life, but the low-temperature performance is poor, the application of the lithium iron phosphate is severely limited, and the low-temperature performance needs to be improved by a certain means urgently. Modification from the material level will increase the material cost and the procedure is complicated.
Disclosure of Invention
The invention aims to provide a cathode material suitable for a low-temperature environment, and the invention improves the electric contact between lithium iron phosphate and a current collector, reduces the contact resistance, reduces the electrode polarization of a cathode and improves the conductivity at low temperature by adding uniformly distributed metal oxides into the lithium iron phosphate.
In order to solve the technical problem, the technical scheme of the invention is as follows: a positive electrode material suitable for a low-temperature environment comprises the following substances in percentage by mass:
Figure BDA0003231841420000011
Figure BDA0003231841420000021
preferably, the metal oxide is one or more of zinc oxide, titanium dioxide and cerium oxide. The zinc oxide, titanium dioxide and cerium oxide substances provided by the invention have stable structures, do not react with the anode and the electrolyte, and can stably exist in a system; zinc oxide (ZnO), titanium dioxide (TiO)2) And cerium oxide (CeO)2) The zinc, titanium and cerium metal has good machinability, the zinc, titanium and cerium metal is soft, the oxide of the zinc, titanium and cerium metal can adapt to the processing of processes such as coating, rolling and the like in the manufacturing of lithium ion batteries, does not produce negative effects on electrode plates, and belongs to ideal additive substances.
Preferably, the positive electrode conductive agent is one or more of graphene, SP, carbon nanotubes and carbon fibers. The binder used by the positive electrode is one or more of polyvinyl alcohol (PVA), Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF) and the like which can improve the binding power of the pole piece, wherein PVDF is preferred, the glass transition temperature of PVDF is-42 ℃, and the positive electrode is suitable for low-temperature systems.
Preferably, the following substances are included according to mass fraction:
Figure BDA0003231841420000022
the positive electrode material with the components and the using amount is matched with small-particle graphite with good low-temperature performance as a negative electrode main material, the particle size D50 of the graphite is 8-12 mu m, the path of lithium ion desorption of the graphite is short, the steric hindrance is small, the positive electrode material is suitable for a low-temperature system, after metal oxide is added to the positive electrode, the dynamic performance is enhanced, the electron desorption speed is increased along with the increase of the positive electrode material, negative minimum particles with high lithium desorption speed are needed to achieve the desorption speed balance between the positive electrode and the negative electrode of the system, and the low-temperature performance of the positive electrode material provided by the invention is effectively ensured.
The invention aims to provide a lithium ion battery suitable for a low-temperature environment, which effectively reduces the internal impedance in the low-temperature environment, improves the charge-discharge efficiency of the battery and prolongs the cycle life.
In order to solve the technical problem, the technical scheme of the invention is as follows: a lithium ion battery suitable for low-temperature environment comprises a positive electrode, a negative electrode, low-temperature electrolyte and a diaphragm; the positive electrode is made of the positive electrode material.
Preferably, the negative electrode active material is graphite. The graphite has good low-temperature performance, and is beneficial to ensuring the low-temperature performance of the battery.
D of preferably graphite50Is 8 mum to 12 μm. The graphite lithium ion deintercalation system has short path and small steric hindrance, is suitable for a low-temperature system, has enhanced dynamic performance after metal oxide is added into the positive electrode, increases the electron deintercalation speed, and needs to be matched with negative minimum particles with higher lithium deintercalation speed so as to achieve the deintercalation speed balance between the positive electrode and the negative electrode of the system.
Preferably, the material for the negative electrode comprises the following substances in percentage by mass:
Figure BDA0003231841420000031
the binding agent is one or more of substances capable of improving the binding power of the pole piece, such as Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA) and the like, wherein the preferred SBR has high adaptability with a graphite system, wide application and stable material properties.
In the invention, the negative electrode conductive agent is the same as the positive electrode conductive agent, and one or more of graphene, SP, carbon nano tubes and carbon fibers are selected;
the binding agent is one or more of substances capable of improving the binding power of the pole piece, such as Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA) and the like, wherein the preferred SBR has high adaptability to a graphite system, wide application and stable material property;
wherein the dispersant is sodium carboxymethylcellulose (CMC)
Wherein the electrolyte is conventional low-temperature electrolyte;
wherein the isolating membrane is a polyethylene isolating membrane with better low-temperature performance and ceramic-coated double surfaces;
preferably, the material for the negative electrode comprises the following substances in percentage by mass:
Figure BDA0003231841420000041
graphite D50And 8 μm.
By adopting the technical scheme, the invention has the beneficial effects that:
according to the invention, metal oxide is dispersed in a lithium iron phosphate material, the particle size of the metal oxide is nano-scale, the lithium iron phosphate is micro-scale, the metal oxide is dispersed in gaps of the lithium iron phosphate, electrons are originally conducted between the materials by virtue of electrolyte at low temperature, but the conductivity of the low-temperature electrolyte is limited, the conductivity of metal substances is not influenced by temperature by virtue of the conduction of the metal oxide in the gaps, and the low-temperature performance can be effectively improved; therefore, on one hand, the addition of the metal oxide effectively improves the electric contact between the lithium iron phosphate and the current collector and reduces the contact resistance; on the other hand, the metal oxide is dispersed among the lithium iron phosphate materials, so that the charge transfer is increased, and the contact resistance among the materials is effectively improved, thereby integrally reducing the electrode polarization of the anode and increasing the conductivity of the anode at low temperature;
according to the low-temperature lithium ion battery provided by the invention, the metal oxide is added into the positive electrode system, so that the electric contact between lithium iron phosphate and a current collector and the electric contact between materials are improved, the contact resistance is reduced, and the conductivity of the positive electrode at low temperature is improved; the small-particle graphite is matched to balance the ion de-intercalation rate between the positive electrode and the negative electrode, so that the cycle life of the battery at low temperature is prolonged;
according to the invention, the anode is doped with the metal oxide capable of improving the low-temperature conductivity of the material, the capability of the anode for releasing and embedding lithium ions at low temperature is improved to a certain extent, and meanwhile, the small-particle graphite cathode is matched, so that the conductivity of the anode and the cathode at low temperature is integrally improved, the macroscopic expression is that the discharge speed at low temperature is improved, and the low-temperature cycle life is prolonged;
the invention is based on the system angle, compares the material modification, has simple process, is easy to realize, and has more obvious improvement effect.
Thereby achieving the above object of the present invention.
Drawings
FIG. 1 is a cycle curve (0.5C/0.5C) at-20 ℃ of lithium ion batteries obtained in examples 1 to 4 of the present invention and comparative example.
Detailed Description
In order to further explain the technical solution of the present invention, the present invention is explained in detail by the following specific examples.
Example 1
The embodiment discloses a cathode material and a lithium ion battery suitable for a low-temperature environment, wherein the cathode and the anode of the lithium ion battery respectively comprise the following components:
positive electrode (mass fraction): 97% of lithium iron phosphate, 1% of zinc oxide, 1% of graphene and 1% of PVA;
negative electrode (mass fraction): 97% of graphite, 1% of graphene, 1% of CMC and 1% of SBR;
graphite D50 was 12 μm.
Example 2
The embodiment discloses a cathode material and a lithium ion battery suitable for a low-temperature environment, wherein the cathode and the anode of the lithium ion battery respectively comprise the following components:
positive electrode (mass fraction): 95% of lithium iron phosphate, 3% of zinc oxide, 1% of SP and 1% of PVA;
negative electrode (mass fraction): 97% graphite, 1% SP, 1% CMC, 1% SB;
graphite D50 was 8 μm.
Example 3
The embodiment discloses a cathode material and a lithium ion battery suitable for a low-temperature environment, wherein the cathode and the anode of the lithium ion battery respectively comprise the following components:
positive electrode (mass fraction): 91% of lithium iron phosphate, 5% of titanium dioxide, 2% of carbon nanotubes and 2% of PTFE;
negative electrode (mass fraction): 93.5% graphite, 2% carbon nanotubes, 1.5% CMC, 3% PAA;
graphite D50 was 10 μm.
Example 4
The embodiment discloses a cathode material and a lithium ion battery suitable for a low-temperature environment, wherein the cathode and the anode of the lithium ion battery respectively comprise the following components:
positive electrode (mass fraction): 87% of lithium iron phosphate, 8% of cerium oxide, 3% of carbon fiber and 3% of PVDF;
negative electrode (mass fraction): 90% of graphite, 3% of carbon fiber, 2% of CMC, and 5% of SBR;
graphite D50 was 8 μm.
Comparative example
In this example, the positive electrode and the negative electrode of the lithium ion battery are respectively composed as follows:
positive electrode (mass fraction): 97% of lithium iron phosphate, 1.5% of graphene and 1.5% of PVDF;
negative electrode (mass fraction): 97% graphite, 1% SP, 1% CMC, 1% SBR.
The starting materials of examples 1 to 4 and comparative example were prepared into lithium ion batteries by the following manufacturing process:
stirring a main material by a positive electrode or a negative electrode, coating, cold pressing, slitting, and preparing a sheet to obtain a pole piece;
preparing a bare cell by laminating or winding the positive and negative pole pieces and the diaphragm, and obtaining an activated finished battery after packaging, liquid injection, standing and formation;
wherein the electrolyte is conventional low-temperature electrolyte;
wherein, the isolating membrane is a polyethylene isolating membrane with better low-temperature performance and ceramic-coated double surfaces.
Conductivity tests were performed on the positive electrode sheets of the batteries of examples 1 to 4 and comparative example using an electrochemical workstation, and the results are detailed in table 1.
Group of Conductivity (S/cm)
Comparative example 5.1x10-9
Example 1 3.1x10-8
Example 2 7.4x10-8
Example 3 8.6x10-8
Example 4 9.3x10-8
As can be seen from table 1, after the metal oxide is added to the lithium iron phosphate, the conductivity of the positive electrode is improved by one order of magnitude, and the conductivity is improved with the increase of the metal oxide, so that it can be proved that the addition of the metal oxide in the positive electrode system improves the electrical contact between the lithium iron phosphate and the current collector and the electrical contact between the lithium iron phosphate and the current collector, and reduces the contact resistance, thereby increasing the conductivity of the positive electrode.
The lithium ion batteries prepared in examples 1 to 4 and comparative example were tested for cycle performance under the following cycle conditions: the ambient temperature was-20 deg.C, and the cycle was measured at 0.5C/0.5C, and the resulting cycle curve is shown in FIG. 1. From the cycling curves, the proposed scheme of the present invention is a great improvement over conventional lithium iron phosphate systems in terms of low temperature cycling. The lithium ion battery obtained in the comparative example has the capacity of only 87 percent after the lithium ion battery is cycled for 200 weeks at the temperature of 20 ℃ below zero; the lithium ion batteries of the embodiments 1 to 4 are cycled for 200 weeks under the same conditions, the capacity residual is more than 92%, and the cycling trend is gentle, so that the scheme provided by the invention effectively reduces the internal impedance, improves the charging and discharging efficiency of the batteries, and prolongs the cycle life.
Comparing example 1 with example 2, it is known that the cycle life of the system can be improved by increasing the amount of the metal oxide under the same condition; the use amount of the metal oxide is increased, the particle size of the negative electrode is reduced under the same condition, the positive electrode and the negative electrode of the system reach the balance of the de-intercalation efficiency, and the system obtained by matching is the same as the embodiment 4, so that the overall performance is improved most obviously, and the cycle effect is optimal.

Claims (9)

1. A positive electrode material suitable for a low-temperature environment is characterized in that: the material comprises the following substances in percentage by mass:
Figure FDA0003231841410000011
2. the positive electrode material suitable for a low-temperature environment according to claim 1, wherein: the metal oxide is one or more of zinc oxide, titanium dioxide and cerium oxide.
3. The positive electrode material suitable for a low-temperature environment according to claim 1, wherein: the positive electrode conductive agent is one or more of graphene, SP, carbon nano tubes and carbon fibers.
4. The positive electrode material suitable for a low-temperature environment according to claim 1, wherein: the material comprises the following substances in percentage by mass:
Figure FDA0003231841410000012
5. a lithium ion battery suitable for low-temperature environment comprises a positive electrode, a negative electrode, low-temperature electrolyte and a diaphragm; the method is characterized in that: the positive electrode is made of the positive electrode material according to any one of claims 1 to 4.
6. The lithium ion battery suitable for a low temperature environment according to claim 5, wherein: the negative active material is graphite.
7. The lithium ion battery suitable for a low temperature environment according to claim 6, wherein: d of graphite508 to 12 μm.
8. The lithium ion battery suitable for a low temperature environment according to claim 5, wherein:
the anode is made of the following materials in percentage by mass:
Figure FDA0003231841410000021
9. the lithium ion battery suitable for a low temperature environment according to claim 5, wherein:
the anode is made of the following materials in percentage by mass:
Figure FDA0003231841410000022
graphite D50And 8 μm.
CN202110989016.XA 2021-08-26 2021-08-26 Anode material suitable for low-temperature environment and lithium ion battery Pending CN113725411A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114824444A (en) * 2022-05-20 2022-07-29 湖南时代联合新能源有限公司 Water-based lithium manganate battery and preparation method thereof
CN115799441A (en) * 2023-02-10 2023-03-14 欣旺达电动汽车电池有限公司 Lithium ion battery and power utilization device

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105390700A (en) * 2015-11-16 2016-03-09 哈尔滨工业大学 Method for modifying positive electrode of lithium ion battery by adding metal oxide/carbon composite material
CN108987705A (en) * 2018-07-17 2018-12-11 深圳市优特利电源有限公司 A kind of electrode material composite, based lithium-ion battery positive plate and lithium ion battery
CN112331833A (en) * 2020-11-10 2021-02-05 江西省汇亿新能源有限公司 Lithium iron phosphate starting battery and manufacturing method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105390700A (en) * 2015-11-16 2016-03-09 哈尔滨工业大学 Method for modifying positive electrode of lithium ion battery by adding metal oxide/carbon composite material
CN108987705A (en) * 2018-07-17 2018-12-11 深圳市优特利电源有限公司 A kind of electrode material composite, based lithium-ion battery positive plate and lithium ion battery
CN112331833A (en) * 2020-11-10 2021-02-05 江西省汇亿新能源有限公司 Lithium iron phosphate starting battery and manufacturing method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114824444A (en) * 2022-05-20 2022-07-29 湖南时代联合新能源有限公司 Water-based lithium manganate battery and preparation method thereof
CN115799441A (en) * 2023-02-10 2023-03-14 欣旺达电动汽车电池有限公司 Lithium ion battery and power utilization device

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Application publication date: 20211130