CN112290079A - Quick-charging lithium ion battery - Google Patents
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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
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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
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- H—ELECTRICITY
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- 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
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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
- H01M4/64—Carriers or collectors
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- 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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- 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
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Abstract
The invention discloses a quick-charging lithium ion battery which comprises an anode, a diaphragm, a cathode and electrolyte, wherein the anode comprises an aluminum foil and an anode main material layer coated on the aluminum foil, and the anode main material layer comprises lithium iron phosphate, a conductive agent and a bonding agent; the negative electrode comprises a copper foil, a negative electrode main material layer and a conductive interlayer positioned in the negative electrode main material layer; wherein the negative electrode main material layer comprises artificial graphite, a conductive agent, a binder and a dispersing agent; according to the invention, the lithium iron phosphate anode is matched with the cathode with the sandwich structure, and 5C charging meets the rapid charging standard.
Description
Technical Field
The invention relates to the technical field of chemical batteries, in particular to a quick-charging lithium ion battery.
Background
For the development of lithium ion batteries, in addition to energy density and safety performance, the charging speed also becomes a key evaluation index. At present, various manufacturers begin to develop fast-charging batteries, and for a fast-charging system, the key is the speed and capacity of a negative electrode for receiving lithium ions. The speed and capacity of the negative electrode for receiving lithium ions are insufficient, so that lithium is easy to be separated from the negative electrode, and the safety accident of the battery is caused by lithium separation. Especially for the coating thickness of the negative electrode more than 600g/cm2According to the thick coating lithium ion battery, the negative electrode layer is not smooth in lithium ion conduction in the thickness direction, the impedance is increased, the charging speed of the battery is low, and the practical application of the lithium ion battery is limited.
Disclosure of Invention
The invention aims to provide a quick-charging lithium ion battery, which utilizes the matching of a lithium iron phosphate anode and a cathode with a sandwich structure, and 5C charging meets the quick-charging standard.
In order to solve the technical problem, the technical scheme of the invention is as follows: a fast-charging lithium ion battery comprises a positive electrode, a diaphragm, a negative electrode and electrolyte, wherein the positive electrode comprises an aluminum foil and a positive electrode main material layer coated on the aluminum foil, and the positive electrode main material layer comprises lithium iron phosphate, a conductive agent and a bonding agent;
the negative electrode comprises a copper foil, a negative electrode main material layer and a conductive interlayer positioned in the negative electrode main material layer;
wherein the negative electrode main material layer comprises artificial graphite, a conductive agent, a binder and a dispersant.
Preferably, a positive conductive coating is further arranged between the aluminum foil and the positive main material layer;
the thickness of the conductive coating of the positive electrode is between 1 and 3 mu m.
The positive conductive coating is prepared by using an electrostatic spinning spraying technology, improves the interface performance, reduces the contact resistance, enhances the bonding strength of the active material and the aluminum foil, and improves the stability of the current collector; the positive conductive coating can help lithium electrons to be quickly removed, so that the positive structure is kept stable, and the electrons can be repeatedly removed and embedded.
The lithium iron phosphate particles D50 are 5-8 μm. The anode of the invention adopts the lithium iron phosphate, and the main purpose of the invention is that the safety performance of the lithium iron phosphate is higher; when the small-particle lithium iron phosphate is used as a lithium ion releasing material, the path is short, the lithium iron phosphate can be quickly released from the anode and conducted into the cathode, and quick charging is favorably realized.
Preferably, the negative electrode main material layer comprises, by mass:
the main material layer of the negative electrode is a common material, and D50 which is generally selected to be between 10 and 25 mu m is convenient for the improvement of the invention in the prior art.
Preferably, the total thickness of the negative electrode main material layer and the conductive interlayer is L, and the distance 1/3L to 1/2L between the side of the conductive interlayer facing the separator and the separator. The position of the conductive interlayer in the present invention has an influence on the rate of intercalation of lithium ions into the negative electrode.
The thickness of the conductive interlayer is 8 to 10 μm. The conductive interlayer has better conductivity than the main layer of the negative electrode, the thicker the interlayer is, the better the conductivity is, but the solid content of the conductive interlayer is low, and the thicker the conductive interlayer is, the lower the integral energy density is.
Preferably, the conductive interlayer comprises the following substances in percentage by mass:
wherein the small-particle artificial graphite D50 is 3-6 μm.
Preferably, a negative conductive coating is arranged between the copper foil and the negative main material layer;
the thickness of the negative electrode conductive coating is between 1 μm and 3 μm.
The negative conductive coating improves the interface performance, reduces the contact resistance, enhances the bonding strength of the active material and the copper foil, and improves the stability of the current collector; the negative electrode conductive coating helps lithium electrons to be rapidly embedded into the negative electrode, so that the structure of the negative electrode is kept stable, and the electrons can be repeatedly de-embedded;
further preferably, the conductive slurry of the positive conductive coating and the conductive slurry of the negative conductive coating comprise one or more of carbon nanotubes, graphene and conductive carbon black.
By adopting the technical scheme, the invention has the beneficial effects that:
1. according to the invention, the conductive interlayer is arranged in the thick-coated cathode main material layer to buffer polarization impedance caused by cathode thick coating, the conductive interlayer is beneficial to lithium ion rapid conduction, the impedance increase caused by unsmooth lithium ion conduction of the cathode layer in the thickness direction is relieved, the conductive interlayer is added, the speed of receiving electrons by the cathode can be increased, namely, the charging speed is increased;
2. according to the lithium ion battery, the cathode with the conductive interlayer is matched with the anode using the lithium iron phosphate, so that the internal resistance of a system is obviously reduced, the safety is improved, the rate capability is obviously improved, the 5C charging capacity retention rate is over 96 percent, and the lithium ion battery meets the standard of quick charging.
Thereby achieving the above object of the present invention.
Drawings
Fig. 1 is a schematic cross-sectional structure diagram of a fast-charging lithium ion battery according to the present invention.
In the figure:
a positive electrode 1; an aluminum foil 11; a positive electrode main material layer 12; a positive electrode conductive coating 13; a diaphragm 2; a negative electrode 3; a copper foil 31; a negative electrode main material layer 32; a conductive interlayer 33; and a negative conductive coating 34.
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 fast-charging lithium ion battery, as shown in fig. 1, which comprises a positive electrode 1, a diaphragm 2, a negative electrode 3 and electrolyte, wherein the positive electrode 1 comprises an aluminum foil 11 and a positive electrode main material layer 12 coated on the aluminum foil 11, and the positive electrode main material layer 12 comprises 97% of lithium iron phosphate, 1% of conductive agent and 2% of adhesive by mass;
the negative electrode 3 comprises a copper foil 31, a negative electrode main material layer 32 and a conductive interlayer 33 positioned in the negative electrode main material layer 32;
the negative electrode main material layer 32 includes, by mass, 95% of artificial graphite, 3% of a conductive agent, 1% of a binder, and 1% of a dispersant.
In this embodiment, a positive conductive coating 13 is further included between the aluminum foil 11 and the positive main material layer 12; the thickness of the positive electrode conductive coating 13 was 1 μm.
In this embodiment, the lithium iron phosphate particles D50 are 5 μm to 8 μm.
The total thickness of the negative electrode main material layer 32 and the conductive interlayer 33 in this embodiment is L, and the distance between the side of the conductive interlayer 33 facing the separator 2 and the separator 2 is 1/2L.
The thickness of the conductive interlayer 33 is 8 μm.
In this embodiment, the conductive interlayer 33 includes the following substances by mass:
92% of small-particle graphite, 4% of conductive agent, 2% of binder and 2% of dispersing agent.
Wherein the small-particle artificial graphite D50 is 3-6 μm.
In this embodiment, a negative conductive coating 34 is further disposed between the copper foil 31 and the negative main material layer 32; the negative electrode conductive coating 34 has a thickness of 1 μm.
In this embodiment, the conductive paste of the positive conductive coating 13 and the negative conductive coating 34 is carbon nanotubes.
The specific preparation method of the battery in this example is as follows:
stirring, coating, cold pressing, stripping and flaking the anode 1 and the cathode 3;
and (3) carrying out a lamination process on the pole pieces of the positive pole 1 and the pole pieces and the diaphragm 2 to obtain a naked battery cell, and carrying out packaging, liquid injection, standing, formation and capacity grading on the naked battery cell to obtain a finished product battery.
Example 2
The main differences between this embodiment and embodiment 1 are:
the positive electrode main material layer 12 comprises 96% of lithium iron phosphate, 2% of a conductive agent and 2% of a binder by mass;
the negative electrode main material layer 32 includes 96% of artificial graphite, 2% of a conductive agent, 1% of a binder, and 1% of a dispersant by mass.
The positive conductive coating 13 and the negative conductive coating 34 are made of graphene, and the thickness of the graphene is 2 micrometers;
the conductive interlayer 33 comprises 93% of small-particle artificial graphite, 3% of a conductive agent, 3% of a binder and 1% of a dispersing agent in percentage by mass; the thickness of the conductive interlayer 33 is 9 μm, and the distance between the side of the conductive interlayer 33 facing the separator 2 and the separator 2 is 5/12L.
The specific preparation method of the battery in this example is as follows:
stirring, coating, cold pressing, stripping and flaking the anode 1 and the cathode 3;
and (3) carrying out a lamination process on the pole pieces of the positive pole 1 and the pole pieces and the diaphragm 2 to obtain a naked battery cell, and carrying out packaging, liquid injection, standing, formation and capacity grading on the naked battery cell to obtain a finished product battery.
Example 3
The main differences between this embodiment and embodiment 1 are:
the positive electrode main material layer 12 includes, in mass fraction: 95% of lithium iron phosphate, 3% of a conductive agent and 2% of a binder;
the negative electrode main material layer 32 includes, in mass fraction: 94% of artificial graphite, 3% of conductive agent, 1% of binder and 2% of dispersant;
SP is selected as the positive conductive coating 13 and the negative conductive coating 34, and the thickness is 3 mu m;
the conductive interlayer 33 comprises 94% of small-particle artificial graphite, 3% of a conductive agent, 1% of a binder and 2% of a dispersing agent in percentage by mass; the conductive interlayer 33 is 10 μm thick, and the distance between the side of the conductive interlayer 33 facing the separator 2 and the separator 2 is 1/3L.
The specific preparation method of the battery in this example is as follows:
stirring, coating, cold pressing, stripping and flaking the anode 1 and the cathode 3;
and (3) carrying out a lamination process on the pole pieces of the positive pole 1 and the pole pieces and the diaphragm 2 to obtain a naked battery cell, and carrying out packaging, liquid injection, standing, formation and capacity grading on the naked battery cell to obtain a finished product battery.
Example 4
The main differences between this embodiment and embodiment 1 are:
the positive electrode main material layer 12 includes, in mass fraction: 95% of lithium iron phosphate, 3% of a conductive agent and 2% of a binder;
the negative electrode main material layer 32 includes, in mass fraction: 93% of artificial graphite, 3% of conductive agent, 2% of binder and 2% of dispersant;
the positive conductive coating 13 and the negative conductive coating 34 are made of graphene, and the thickness of the graphene is 2 micrometers;
the conductive interlayer 33 comprises 95% of small-particle artificial graphite, 2% of a conductive agent, 1.5% of a binder and 1.5% of a dispersing agent in mass percentage;
the thickness of the conductive interlayer 33 is 9 μm, and the distance between the side of the conductive interlayer 33 facing the separator 2 and the separator 2 is 1/3L.
The specific preparation method of the battery in this example is as follows:
stirring, coating, cold pressing, stripping and flaking the anode 1 and the cathode 3;
and (3) carrying out a lamination process on the pole pieces of the positive pole 1 and the pole pieces and the diaphragm 2 to obtain a naked battery cell, and carrying out packaging, liquid injection, standing, formation and capacity grading on the naked battery cell to obtain a finished product battery.
Comparative example 1
The ternary system of the conductive coating and the conductive interlayer 33 is absent in this example:
the positive electrode main material layer 12 includes, in mass fraction: 96.5% of ternary material NCM523, 2% of conductive agent and 1.5% of binder;
the negative electrode main material layer 32 includes, in mass fraction: 95.5 percent of artificial graphite, 1.5 percent of conductive agent, 1 percent of binder and 2 percent of dispersant.
The specific preparation method of the battery in this example is as follows:
stirring, coating, cold pressing, stripping and flaking the anode 1 and the cathode 3;
and (3) carrying out a lamination process on the pole pieces of the positive pole 1 and the pole pieces and the diaphragm 2 to obtain a naked battery cell, and carrying out packaging, liquid injection, standing, formation and capacity grading on the naked battery cell to obtain a finished product battery.
Comparative example 2
This example uses a lithium iron phosphate system designed with no conductive coating and conductive interlayer 33:
the positive electrode main material layer 12 includes, in mass fraction: 96.5% of lithium iron phosphate, 2% of conductive agent and 1.5% of binder;
the negative electrode main material layer 32 includes, in mass fraction: 95.5 percent of artificial graphite, 1.5 percent of conductive agent, 1 percent of binder and 2 percent of dispersant.
The specific preparation method of the battery in this example is as follows:
stirring, coating, cold pressing, stripping and flaking the anode 1 and the cathode 3;
and (3) carrying out a lamination process on the pole pieces of the positive pole 1 and the pole pieces and the diaphragm 2 to obtain a naked battery cell, and carrying out packaging, liquid injection, standing, formation and capacity grading on the naked battery cell to obtain a finished product battery.
The finished batteries obtained in examples 1 to 4 and comparative examples 1 and 2 were subjected to electrical property tests and safety property tests, the test results are shown in tables 1 and 2, and the specific test methods are as follows:
1. charge rate test
Respectively testing the charging capacity of each group of batteries under the charging of 0.5C, 1C, 2C, 3C, 4C and 5C multiplying power, and comparing the charging performance by taking 0.5C as a reference;
2. internal resistance test
Testing the DCR of each group of batteries during 3C charging at normal temperature by using a dynamic DCR testing method;
3. impact test
The test sample cell was placed on a flat surface. A 7.9mm (5/16 inch) diameter rod was placed crosswise over the center of the sample. A9.1 KG (20 pound) weight was dropped onto the sample from a height of 61cm (2 feet) and the cell was observed.
Table 1 examples 1 to 4 and comparative examples 1 and 2 give the results of the charge rate test of the finished batteries
Table 2 results of internal resistance test and safety test of finished batteries obtained in examples 1 to 4 and comparative examples 1 and 2
| Group of | Internal resistance/m omega | Safety test results |
| Comparative example 1 | 35 | Fire and explosion prevention |
| Comparative example 2 | 32 | Without ignition and explosion |
| Example 1 | 23 | Without ignition and explosion |
| Example 2 | 24 | Without ignition and explosion |
| Example 3 | 22 | Without ignition and explosion |
| Example 4 | 21 | Without ignition and explosion |
As can be seen from the comparison of the data in tables 1 and 2, the lithium iron phosphate system has better safety performance than the ternary system, and when the safety test is carried out, the lithium iron phosphate system does not catch fire or explode, and the battery has better safety performance when the lithium iron phosphate system is selected;
after the invention is adopted, the DCR of the system is obviously reduced, which shows that the design of the conductive coating and the design of the conductive interlayer 33 can improve the electronic conductivity of the system, so that lithium ions can be rapidly de-intercalated, and the polarization caused by insufficient dynamic performance is reduced, thereby obviously reducing the DCR of the system;
the charging rate data shows that the design of the conductive coating provided by the invention and the conductive interlayer 33 of the cathode 3 can effectively improve the charging rate performance of a system, and the battery manufactured by the invention meets the 5C charging, has the 5C charging capacity retention rate of more than 96 percent and meets the standard of quick charging.
The above embodiments and drawings are not intended to limit the form and style of the present invention, and any suitable changes or modifications thereof by those skilled in the art should be considered as not departing from the scope of the present invention.
Claims (9)
1. The utility model provides a quick lithium ion battery that charges, includes positive pole, diaphragm, negative pole and electrolyte, its characterized in that:
the anode comprises an aluminum foil and an anode main material layer coated on the aluminum foil, and the anode main material layer comprises lithium iron phosphate, a conductive agent and a bonding agent;
the negative electrode comprises a copper foil, a negative electrode main material layer and a conductive interlayer positioned in the negative electrode main material layer;
wherein the negative electrode main material layer comprises artificial graphite, a conductive agent, a binder and a dispersant.
2. A fast-charging lithium ion battery as claimed in claim 1, characterized in that: a positive conductive coating is also arranged between the aluminum foil and the positive main material layer;
the thickness of the conductive coating of the positive electrode is between 1 and 3 mu m.
3. A fast-charging lithium ion battery as claimed in claim 1, characterized in that: the lithium iron phosphate particles D50 are 5-8 μm.
4. A fast-charging lithium ion battery as claimed in claim 1, characterized in that: the negative electrode main material layer comprises the following components in percentage by mass:
5. a fast-charging lithium ion battery as claimed in claim 1, characterized in that:
the total thickness of the negative electrode main material layer and the conductive interlayer is L, and the distance between one side of the conductive interlayer facing the separator and the separator is 1/3L-1/2L.
6. A fast-charging lithium ion battery as claimed in claim 1, characterized in that: the thickness of the conductive interlayer is 8 to 10 μm.
7. A fast-charging lithium ion battery as claimed in claim 1, characterized in that: the conductive interlayer comprises the following substances in percentage by mass:
wherein the small-particle artificial graphite D50 is 3-6 μm.
8. A fast-charging lithium ion battery as claimed in claim 1, characterized in that: a negative conductive coating is arranged between the copper foil and the negative main material layer;
the thickness of the negative electrode conductive coating is between 1 μm and 3 μm.
9. A fast-charging lithium-ion battery as claimed in claim 2 or 8, characterized in that: the conductive slurry of the positive conductive coating and the negative conductive coating comprises one or more of carbon nano tubes, graphene and conductive carbon black.
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Application publication date: 20210129 |