CN114520364A - High-rate ternary manganese-doped system starting type lithium ion battery - Google Patents
High-rate ternary manganese-doped system starting type lithium ion battery Download PDFInfo
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- CN114520364A CN114520364A CN202210142196.2A CN202210142196A CN114520364A CN 114520364 A CN114520364 A CN 114520364A CN 202210142196 A CN202210142196 A CN 202210142196A CN 114520364 A CN114520364 A CN 114520364A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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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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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
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- 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
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- 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
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Abstract
The invention belongs to the technical field of batteries, and particularly relates to a high-rate ternary manganese-doped system starting type lithium ion battery which comprises a battery shell, an anode, a cathode, a diaphragm and electrolyte, wherein the anode and the cathode are arranged on the battery shell; the positive electrode comprises 70-100 parts of positive active substances, 0.8-1.7 parts of positive adhesive and 0.5-4.5 parts of positive conductive agent, wherein the positive active substances comprise 55-70 parts of nickel-cobalt-manganese ternary material and 15-30 parts of lithium manganate, and the content ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary material is 8: 1: 1; the negative electrode comprises 91-98 parts of negative electrode active material, 2.3-4.2 parts of negative electrode adhesive and 0.5-4.5 parts of negative electrode conductive agent. The invention has the technical effects that: the positive electrode adopts a system of nickel-cobalt-manganese ternary material doped with lithium manganate material, so that the proportion and the use of cobalt-containing material are reduced, and the cost of the battery is reduced.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a high-rate ternary manganese-doped system starting type lithium ion battery.
Background
In the prior art, a start-up type high-rate lithium ion battery generally adopts a ternary system laminated lithium ion battery, wherein the ternary system lithium ion battery comprises a positive active material, a positive adhesive and a positive conductive agent which form a positive electrode, and a negative active material, a negative adhesive and a negative conductive agent which form a negative electrode, and the positive active material comprises 91-98 parts of nickel, cobalt and manganese, and the content ratio of the nickel, the cobalt and the manganese is 5: 2:3, the anode adhesive comprises 0.8-1.7 parts of polyvinylidene fluoride, the anode conductive agent comprises 0.5-1.5 parts of carbon nano tubes and 0-3 parts of superfine carbon powder SP, the cathode active material comprises one or the combination of more than two of 91-98 parts of artificial graphite, natural graphite and composite graphite, the cathode adhesive comprises 0.8-1.7 parts of carboxymethyl cellulose and 1.5-2.5 parts of styrene butadiene rubber, and the cathode conductive agent comprises 0.5-1.5 parts of carbon nano tubes and 0-3 parts of superfine carbon powder SP. The problem is that the ternary system lithium ion battery has a large proportion of cobalt, high cost and certain limitation, so that a novel lithium ion battery which can reduce the usage amount of cobalt and the material cost and keep the performance close to that of the traditional lithium cobaltate system lithium ion battery is needed to be designed.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a high-rate ternary manganese-doped system starting type lithium ion battery, wherein a nickel-cobalt-manganese ternary material doped lithium manganate material system is adopted as a positive electrode, the proportion and the use of cobalt-containing materials are reduced, and the battery cost is reduced.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a high-rate ternary manganese-doped system starting type lithium ion battery comprises a battery shell, an anode and a cathode which are arranged on the battery shell, a diaphragm for separating the anode and the cathode, and electrolyte filled in the battery shell;
the positive electrode comprises 70-100 parts of positive active substances, 0.8-1.7 parts of positive adhesive and 0.5-4.5 parts of positive conductive agent, wherein the positive active substances comprise 55-70 parts of nickel-cobalt-manganese ternary material and 15-30 parts of lithium manganate, and the content ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary material is 8: 1: 1;
the negative electrode comprises 91-98 parts of negative electrode active material, 2.3-4.2 parts of negative electrode adhesive and 0.5-4.5 parts of negative electrode conductive agent, wherein the negative electrode active material comprises one or the combination of more than two of artificial graphite, natural graphite and composite graphite.
Further, the positive electrode binder comprises 0.8-1.7 parts of polyvinylidene fluoride.
Further, the positive electrode conductive agent comprises 0.5-1.5 parts of carbon nano tubes and 0-3 parts of superfine carbon powder SP.
Further, the negative electrode adhesive comprises 0.8-1.7 parts of carboxymethyl cellulose and 1.5-2.5 parts of styrene-butadiene rubber.
Further, the negative electrode conductive agent comprises 0.5-1.5 parts of carbon nano tubes and 0-3 parts of superfine carbon powder SP.
The invention has the following beneficial effects:
in the high-rate ternary manganese-doped system starting type lithium ion battery, the anode adopts a system of a nickel-cobalt-manganese ternary material doped lithium manganate material, so that the proportion and the use of the cobalt-containing material are reduced, and the material cost of the battery is reduced.
Drawings
Fig. 1 is a discharge curve diagram of a high-rate ternary manganese-doped system starting type lithium ion battery and a ternary system lithium ion battery.
Fig. 2 is a discharge cycle curve of a high-rate ternary manganese-doped system start-up type lithium ion battery 50A.
Fig. 3 is a discharge cycle curve for a ternary system lithium ion battery cell 50A.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention.
Referring to fig. 1-3, the high-rate ternary manganese-doped system startup lithium ion battery comprises a battery case, a positive electrode and a negative electrode which are arranged on the battery case, a diaphragm for separating the positive electrode and the negative electrode, and electrolyte filled in the battery case, wherein the electrolyte is rate electrolyte;
the positive electrode comprises 70-100 parts of positive active substance, 0.8-1.7 parts of positive adhesive and 0.5-4.5 parts of positive conductive agent, wherein the positive active substance comprises 55-70 parts of nickel-cobalt-manganese ternary material and 15-30 parts of lithium manganate, and the content ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary material is 8: 1: 1;
the positive pole adopts the system that nickel cobalt manganese ternary material dopes lithium manganate material, reduces the proportion and the use that contain the cobalt material, reduces battery material cost, and the capacity of electric core is guaranteed in nickel cobalt manganese ternary material's use, and the performance of electric core discharge platform can be promoted in lithium manganate material's use, and nickel cobalt manganese ternary material and lithium manganate's doping use can have both advantages concurrently.
The negative electrode comprises 91-98 parts of negative electrode active material, 2.3-4.2 parts of negative electrode adhesive and 0.5-4.5 parts of negative electrode conductive agent, wherein the negative electrode active material comprises one or the combination of more than two of artificial graphite, natural graphite and composite graphite.
In one embodiment, the positive electrode binder includes 0.8 to 1.7 parts of polyvinylidene fluoride.
In one embodiment, the positive electrode conductive agent comprises 0.5-1.5 parts of carbon nanotubes and 0-3 parts of ultrafine carbon powder SP.
In one embodiment, the negative electrode binder comprises 0.8-1.7 parts of carboxymethyl cellulose and 1.5-2.5 parts of styrene butadiene rubber.
In one embodiment, the negative conductive agent comprises 0.5-1.5 parts of carbon nanotubes and 0-3 parts of ultrafine carbon powder SP.
The preparation method of the high-rate ternary manganese-doped system starting type lithium ion battery comprises the following steps:
1. respectively preparing a positive electrode material and a negative electrode material according to the weight part parameters;
2. cutting tabs at specific positions on the positive electrode material and the negative electrode material through laser cutting or a hardware cutting die to manufacture positive and negative electrode strip sheet materials or coil materials;
3. winding the manufactured positive and negative strip sheets or coils into a winding core with aligned positive lugs by a semi-automatic winding machine or a full-automatic winding machine, and obtaining a multi-lug winding core after core pressing and shaping;
4. and performing tab spot welding, assembling, liquid injection, formation, secondary sealing and packaging on the winding core, and finally manufacturing a finished product battery core.
The winding mode has the advantages that the production efficiency is far higher than that of the traditional Z-shaped lamination mode, the winding process is more stable, and the consistency is high.
The following describes specific parts of materials and test data of the high-rate ternary manganese-doped system start-up lithium ion battery by using a specific embodiment of the invention:
example one
The high-rate ternary manganese-doped system starting type lithium ion battery comprises a battery shell, a positive electrode and a negative electrode which are arranged on the battery shell, a diaphragm for separating the positive electrode from the negative electrode, and electrolyte filled in the battery shell, wherein the electrolyte is high-rate electrolyte;
the positive electrode comprises 80 parts of positive active material, 1 part of positive adhesive and 3 parts of positive conductive agent;
the positive active substance comprises 60 parts of nickel-cobalt-manganese ternary material and 20 parts of lithium manganate, wherein the content ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary material is 8: 1: 1;
the positive adhesive comprises 1 part of polyvinylidene fluoride;
the positive electrode conductive agent comprises 1 part of carbon nano tube and 2 parts of superfine carbon powder SP;
the negative electrode comprises 95 parts of negative electrode active material, 3 parts of negative electrode adhesive and 3 parts of negative electrode conductive agent;
the negative active material comprises three combinations of artificial graphite, natural graphite and composite graphite;
the negative electrode adhesive comprises 1 part of carboxymethyl cellulose and 2 parts of styrene butadiene rubber;
the negative electrode conductive agent comprises 1 part of carbon nano tube and 2 parts of superfine carbon powder SP.
By adopting the scheme, the high-rate ternary manganese-doped system starting lithium ion battery with the internal resistance of 2.7-2.8m omega and the 1C capacity of more than or equal to 1700mAh can be manufactured, in the embodiment, the high-rate ternary manganese-doped system starting lithium ion battery with the internal resistance of 2.8m omega is adopted for detection, and the discharge detection table of the constant-current battery is 1:
| serial number | 1 | 2 | 3 | 4 |
| Set current mA | 1700 | 34000 | 42500 | 50000 |
| Setting the lower limit |
3000 | 3000 | 3000 | 3000 |
| |
4200 | 4200 | 4200 | 4200 |
| |
4200 | 4200 | 4200 | 4200 |
| Initial temperature of detection point | 26.7 | 26.3 | 26.7 | 26.4 |
| Detection Point end temperature C | 26.5 | 27.4 | 27.7 | 27.2 |
| Average temperature of detection points | 26.5 | 26.7 | 27 | 26.6 |
| Highest temperature of detection point | 26.8 | 27.4 | 27.7 | 27.2 |
| End time Min | 62.49 | 3 | 2.38 | 2.01 |
| Termination capacity mAh | 1770.03 | 1692.64 | 1678.48 | 1661.83 |
In the comparative example, the ternary system lithium ion battery comprises a battery shell, a positive electrode and a negative electrode which are arranged in the battery shell, a diaphragm for separating the positive electrode from the negative electrode and electrolyte filled in the battery shell, wherein the electrolyte is a multiplying power type electrolyte, the positive electrode of the lithium cobaltate system lithium ion battery comprises a positive active material, a positive adhesive and a positive conductive agent, and the negative electrode of the ternary system lithium ion battery comprises a negative active material, a negative adhesive and a negative conductive agent;
the positive active material comprises 95 parts of nickel, cobalt and manganese with the content ratio of 5: 2:3 of nickel-cobalt-manganese ternary material;
the positive adhesive comprises 1 part of polyvinylidene fluoride;
The positive electrode conductive agent comprises 1 part of carbon nano tube and 2 parts of superfine carbon powder SP;
the negative active material comprises 95 parts of combination of three of artificial graphite, natural graphite and composite graphite;
the negative electrode adhesive comprises 1 part of carboxymethyl cellulose and 2 parts of styrene butadiene rubber;
the negative electrode conductive agent comprises 1 part of carbon nano tube and 2 parts of superfine carbon powder SP;
the ternary system lithium ion battery with the internal resistance of 2.7-2.9m omega and the 1C capacity of more than or equal to 1700mAh can be prepared by adopting the parameters of the parts by weight of the materials, and the discharge detection table 2 of the constant-current battery is as follows by using the ternary system lithium ion battery with the internal resistance of 2.8m omega for detection:
| serial number | 5 | 6 | 7 | 8 |
| Set current mA | 1700 | 34000 | 42500 | 50000 |
| Setting the lower limit |
3000 | 3000 | 3000 | 3000 |
| Initial voltage mV | 4197 | 4197 | 4197 | 4198 |
| Maximum voltage mV | 4197 | 4197 | 4197 | 4198 |
| Initial temperature of detection point | 26.6 | 27.1 | 26.7 | 26.9 |
| Detection Point end temperature C | 27.2 | 41.3 | 43.8 | 45.3 |
| Average temperature of detection points | 26.7 | 34.3 | 35 | 35.5 |
| Highest temperature of detection point | 27.2 | 41.3 | 43.8 | 45.3 |
| End time Min | 63.1 | 2.91 | 2.27 | 1.86 |
| Termination capacity mAh | 1787.28 | 1645.43 | 1595.7 | 1536.59 |
When the battery is discharged, when the discharge voltage is lower than the set lower limit end voltage mV, the detection is finished, and the detection point of the battery temperature is positioned on the outer side surface of the battery.
Referring to fig. 1, by comparing serial numbers 1 and 5 in tables 1 and 2, when the discharge current of the battery is 1700mA, the termination temperature, average temperature, and maximum temperature of the high-rate ternary manganese-doped system start-up type lithium ion battery are slightly superior to the corresponding performances of the ternary system lithium ion battery, and the termination capacity of the high-rate ternary manganese-doped system start-up type lithium ion battery is close to that of the ternary system lithium ion battery, and the high-rate ternary manganese-doped system start-up type lithium ion battery is suitable for replacing the ternary system lithium ion battery in the scene that the discharge current of the battery is 1700 mA;
Through comparison between serial numbers 2 and 6, between serial numbers 3 and 7, and between serial numbers 4 and 8 of tables 1 and 2, the termination temperature, the average temperature, and the highest temperature of the high-rate ternary manganese-doped system startup type lithium ion battery are all significantly lower than those of the ternary system lithium ion battery, the temperature change in the discharge process of the high-rate ternary manganese-doped system startup type lithium ion battery is not significant, the temperature is not higher than 30 ℃, and the termination capacity of the high-rate ternary manganese-doped system startup type lithium ion battery is higher than that of the ternary system lithium ion battery, so the discharge current of the battery is higher than 34000mA, the requirement on the battery temperature is high, or in a scene lacking a better heat dissipation condition, the high-rate ternary manganese-doped system startup type lithium ion battery can be used for replacing the ternary system lithium ion battery.
The comparison of the detection data of the cycle times and the cycle capacity of the high-rate ternary manganese-doped system starting type lithium ion battery and the ternary system lithium ion battery is shown in the table 3 below, and the discharge current during the cycle test is 50000 mA:
by comparing table 3 with fig. 2 and 3, the capacity retention rate performance of the high-rate ternary manganese-doped system start-up type lithium ion battery is close to that of the ternary system lithium ion battery after cyclic charge and discharge.
The foregoing is a preferred embodiment of the present invention, and the basic principles, main features and advantages of the present invention are shown and described. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the present invention, but various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.
Claims (5)
1. A high-rate ternary manganese-doped system starting type lithium ion battery is characterized by comprising a battery case, a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the positive electrode and the negative electrode are arranged on the battery case;
the positive electrode comprises 70-100 parts of positive active substances, 0.8-1.7 parts of positive adhesive and 0.5-4.5 parts of positive conductive agent, wherein the positive active substances comprise 55-70 parts of nickel-cobalt-manganese ternary material and 15-30 parts of lithium manganate, and the content ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary material is 8: 1: 1;
the negative electrode comprises 91-98 parts of negative electrode active material, 2.3-4.2 parts of negative electrode adhesive and 0.5-4.5 parts of negative electrode conductive agent, wherein the negative electrode active material comprises one or the combination of more than two of artificial graphite, natural graphite and composite graphite.
2. The high-rate ternary manganese-doped system startup lithium ion battery of claim 1, wherein the positive electrode binder comprises 0.8-1.7 parts of polyvinylidene fluoride.
3. The high-rate ternary manganese-doped system startup type lithium ion battery according to claim 1, wherein the positive electrode conductive agent comprises 0.5-1.5 parts of carbon nanotubes and 0-3 parts of ultrafine carbon powder SP.
4. The high-rate ternary manganese-doped system startup type lithium ion battery according to claim 1, wherein the negative electrode binder comprises 0.8-1.7 parts of carboxymethyl cellulose and 1.5-2.5 parts of styrene-butadiene rubber.
5. The high-rate ternary manganese-doped system start-up lithium ion battery as claimed in claim 1, wherein the negative electrode conductive agent comprises 0.5-1.5 parts of carbon nanotubes and 0-3 parts of ultrafine carbon powder SP.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117712459A (en) * | 2023-12-08 | 2024-03-15 | 广东佳成新能源有限公司 | High-safety semi-solid battery cell, preparation method thereof and application thereof in field of electronic cigarette batteries |
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| CN107749478A (en) * | 2016-10-21 | 2018-03-02 | 万向二三股份公司 | A kind of LiMn2O4 ternary power lithium ion battery |
| CN109286008A (en) * | 2018-09-25 | 2019-01-29 | 惠州亿纬锂能股份有限公司 | A kind of low-temperature lithium ion battery and preparation method thereof |
| CN113745639A (en) * | 2021-07-23 | 2021-12-03 | 天津力神电池股份有限公司 | Lithium ion battery for 48V start-stop hybrid power and preparation method thereof |
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Patent Citations (5)
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| CN104103848A (en) * | 2013-04-02 | 2014-10-15 | 深圳普益电池科技有限公司 | Lithium manganate and nickel cobalt lithium manganate power battery and manufacturing method thereof |
| CN107749478A (en) * | 2016-10-21 | 2018-03-02 | 万向二三股份公司 | A kind of LiMn2O4 ternary power lithium ion battery |
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| CN109286008A (en) * | 2018-09-25 | 2019-01-29 | 惠州亿纬锂能股份有限公司 | A kind of low-temperature lithium ion battery and preparation method thereof |
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