CN114899380A - Preparation method of lithium iron phosphate lithium ion battery with long service life - Google Patents
Preparation method of lithium iron phosphate lithium ion battery with long service life Download PDFInfo
- Publication number
- CN114899380A CN114899380A CN202210532972.XA CN202210532972A CN114899380A CN 114899380 A CN114899380 A CN 114899380A CN 202210532972 A CN202210532972 A CN 202210532972A CN 114899380 A CN114899380 A CN 114899380A
- Authority
- CN
- China
- Prior art keywords
- iron phosphate
- starch
- lithium ion
- ion battery
- organic alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
Abstract
The invention discloses a preparation method of a long-life lithium iron phosphate lithium ion battery cathode material, wherein the lithium iron phosphate battery cathode is a coated carbon cathode, the inside of particles of the lithium iron phosphate battery cathode is a carbon material with high Poisson ratio, the outside of the particles is coated with a carbon material with low Poisson ratio, after the carbon cathode material is coated, the change of the Poisson ratio of the outer layer of the cathode material is realized, the crack formation and the gradual growth deterioration of the cathode material caused by diffusion stress in the charging and discharging processes of the battery are relieved, and thus the long-life lithium iron phosphate lithium ion battery cathode material is prepared.
Description
Technical Field
The invention belongs to the technical field of lithium ions, and particularly relates to a preparation method of a lithium iron phosphate lithium ion battery with a long service life.
Background
The lithium iron phosphate lithium ion battery is considered to be the most suitable lithium ion battery for an energy storage power station in a photovoltaic power station and a wind power station due to the advantages of long cycle life, high safety, low price and the like.
At present, most of battery cathode materials used are carbon materials, and cracks are gradually formed and pulverized on the surfaces of the carbon materials used in the charge-discharge cycle process due to the diffusion stress of lithium ions, so that the available capacity of the battery is attenuated, and the service life of the battery is shortened. For particles of carbon material, the stress has zero radial component and the maximum value of the surface stress in the tangential direction
，
Where E is the Young's modulus, v is the Poisson's ratio of the electrode material, Ω is the partial molar volume of the solvent (referred to herein as carbon material), and D is the mass transfer factor in the solid phase.
That is, the regulation and control of the diffusion stress of lithium ions on the surface of the carbon negative electrode material can be realized by changing the mechanical properties of the carbon material, and the main solution in the current commercial production is to produce carbon negative electrode materials with different mechanical properties, including hard carbon materials, soft carbon materials and graphite. In the prior art, such as the Chinese patent application publication with the publication number of CN111204731A, the publication time of 2020, 5 and 29 days and the name of 'a preparation method of a hard carbon negative electrode material of a sodium ion battery', the technical scheme recorded in the prior art aims at the defects of low capacity and low first coulombic efficiency of the current battery negative electrode material, and the used raw material coffee grounds are waste residues after coffee bean treatment, so that the high-performance hard carbon material is prepared. And as the Chinese patent application publication with publication No. CN111029578A, publication time of 2021, 4/23/3, entitled "a modified hard carbon negative electrode material and a preparation method thereof", the technical scheme described in the invention adopts a lithiation modification method, which can significantly reduce the specific surface area of the obtained hard carbon material, adjust the pore structure and improve the interfacial activity of the material. And the Chinese patent application publication No. CN112652767A, published at 2021, 4 and 13 days, entitled "a method for preparing a soft carbon anode material for a lithium ion battery", the method for preparing the soft carbon anode material by using prebaked anode waste as a raw material has the advantages of cost saving, environmental protection and simple preparation process. However, the preparation or modification of the negative electrode material by the method is based on single material preparation or modification by physical and chemical reaction of the single material, and the method does not relate to composite coating of multiple carbon materials to prepare the negative electrode material and cannot simultaneously exert the advantages of different carbon materials.
Disclosure of Invention
The invention aims to provide a carbon material battery cathode subjected to special coating treatment aiming at the defects of the prior art, wherein the carbon material with high Poisson ratio is coated inside particles of the carbon material, and the carbon material with low Poisson ratio is coated outside the particles, so that the diffusion stress protection of the carbon material on the outer layer of the cathode to the carbon material inside the cathode in the charging and discharging process of the battery is realized, the crack formation and the gradual growth of the crack of the cathode material caused by the diffusion stress in the charging and discharging process of the battery are reduced, and the consumption of active lithium of the battery in the charging and discharging process is reduced, so that the long-life lithium iron phosphate lithium ion battery cathode material is prepared.
The invention provides a preparation method of a lithium iron phosphate lithium ion battery with long service life, which comprises an internal material manufacturing step, a coating step and a battery manufacturing step;
the manufacturing method of the inner material comprises the following steps: firstly, coarsely crushing petroleum coke by using a crusher, then crushing the petroleum coke in a ball mill, crushing the petroleum coke in the ball mill to a preset size, then transferring the crushed petroleum coke into a tubular furnace, heating the petroleum coke to 800-1000 ℃ in an inert gas atmosphere, preserving the heat for 1-2 hours, and then cooling the petroleum coke to room temperature to prepare a battery cathode carbon material;
preferably, in the inner material manufacturing step, when the coarse-broken petroleum coke is broken by the ball mill, the rotating speed of the ball mill is set to be 150 r/min-180 r/min.
Further, in the step of manufacturing the inner material, after the coarse-broken petroleum coke is broken by the ball mill, the petroleum coke is broken into particles of 10-15 um, namely the particles with the predetermined size.
More preferably, in the inner material manufacturing step, the inert gas in the tube furnace is nitrogen, argon, or a mixed gas of the two gases.
In the coating step, hot water, organic alcohol and starch are prepared into a starch turbid liquid according to a preset ratio, the battery negative electrode carbon material prepared in the inner material preparation step is placed in the starch turbid liquid to be uniformly stirred and dried into powder at the temperature of 70-80 ℃ and under the inert gas atmosphere, the obtained powder is placed in a tubular furnace, the temperature is heated to 1200-1300 ℃ in the inert gas atmosphere, the temperature is kept for 1-2 hours, and then the temperature is reduced to room temperature, so that the coating of the battery negative electrode carbon material is completed;
further, in the coating step, hot water, organic alcohol and starch are adopted to prepare a starch turbid liquid according to a predetermined ratio, specifically:
firstly, preparing a starch turbid solution, wherein the preparation process comprises the steps of heating water to 60-80 ℃, continuously stirring, and slowly adding organic alcohol into the water until the concentration of the organic alcohol in the water reaches 0.1-0.2 mol/L to obtain an organic alcohol water solution;
and then slowly adding starch into the organic alcohol aqueous solution until the adding amount of the starch in the organic alcohol aqueous solution reaches 1000-1200 g/L, and continuously stirring in the process of adding the starch into the organic alcohol aqueous solution until the starch and the organic alcohol aqueous solution form uniform liquid.
More specifically, in the coating step, the organic alcohol is ethylene glycol, glycerol or a mixed liquid of two alcohols.
And in the battery manufacturing step, the battery cathode carbon material processed in the coating step is used as a cathode of the lithium iron phosphate lithium ion battery to manufacture the lithium iron phosphate lithium ion battery.
After the coating method is used for processing, the diffusion stress protection of the negative electrode outer layer carbon material on the internal carbon material in the battery charging and discharging process is realized, the crack formation and the gradual growth of the crack of the negative electrode material caused by the diffusion stress in the battery charging and discharging process are slowed down, and the consumption of active lithium in the battery in the charging and discharging process is slowed down, so that the long-life lithium iron phosphate lithium ion battery negative electrode material is prepared.
Compared with the prior art, the invention has the beneficial effects that:
1. most of the lithium ion battery negative electrode materials in the industry at present are single hard carbon, soft carbon or graphite, the mechanical property and the charge and discharge property of the materials can not be unified at the same time, and after the soft carbon particles are coated with the hard carbon for treatment, a battery charge and discharge platform made of the soft carbon materials can be ensured, and the structure of the materials in the charge and discharge process can be kept stable all the time by using the mechanical property of the hard carbon.
2. The materials adopted by the coating of the method are starch and organic alcohol of industrial products, the price is low, the materials are easy to obtain, the performance is stable, and the probability of batch difference is low.
3. The coating process has the advantages of low investment on operating equipment, simple process operation steps and low manufacturing cost of materials, so the materials have high economic value.
Drawings
The foregoing and following detailed description of the invention will be more apparent when read in conjunction with the following drawings, in which:
fig. 1 is a schematic structural diagram of a negative electrode carbon material coated outside particles.
Detailed Description
The technical solutions for achieving the objects of the present invention are further illustrated by the following specific examples, and it should be noted that the technical solutions claimed in the present invention include, but are not limited to, the following examples.
As a specific embodiment of the present invention, this example provides a method for preparing a long-life lithium iron phosphate lithium ion battery, which includes an internal material manufacturing step, a coating step, and a battery manufacturing step.
Specifically, the manufacturing method of the inner material comprises the steps of firstly roughly crushing petroleum coke by using a crusher, then crushing the petroleum coke in a ball mill, setting the rotating speed of the ball mill to be 150 r/min-180 r/min, crushing the petroleum coke into particles of 10 um-15 um, then transferring the particles into a tubular furnace, heating the particles to 800-1000 ℃ in an inert gas atmosphere, preserving the heat for 1-2 hours, and then cooling the particles to room temperature to prepare the battery cathode carbon material, wherein the inert gas is nitrogen, argon or a mixed gas of two gases.
The coating step comprises the steps of firstly preparing a starch turbid solution, wherein the preparation process comprises the steps of heating water to 60-80 ℃, continuously stirring, slowly adding organic alcohol into the water until the concentration of the organic alcohol in the water reaches 0.1-0.2 mol/L, and obtaining an organic alcohol water solution, wherein the organic alcohol is ethylene glycol, glycerol or a mixed liquid of two alcohols; and then slowly adding starch into the organic alcohol aqueous solution until the adding amount of the starch in the organic alcohol aqueous solution reaches 1000-1200 g/L, and continuously stirring in the process of adding the starch into the organic alcohol aqueous solution until the starch and the organic alcohol aqueous solution form uniform liquid. Placing the battery negative electrode carbon material prepared in the inner material preparation step into the starch turbid liquid, uniformly stirring, drying at the temperature of 70-80 ℃ and under the inert gas atmosphere condition to form powder, placing the obtained powder into a tubular furnace, heating to 1200-1300 ℃ in the inert gas atmosphere, preserving heat for 1-2 hours, and cooling to room temperature to complete coating of the battery negative electrode carbon material;
and in the battery manufacturing step, the battery cathode carbon material processed in the coating step is used as a cathode of the lithium iron phosphate lithium ion battery to manufacture the lithium iron phosphate lithium ion battery.
TABLE 1
Referring to the above method, 7 kinds of negative electrode sheets that can be used for manufacturing lithium iron phosphate lithium ion batteries are prepared and compared with the negative electrode sheet prepared by the prior art, and specifically, parameters in the process of the electrode sheet prepared by the method are as shown in table 1 above.
The pole pieces are respectively assembled into lithium iron phosphate lithium ion batteries with the same capacity, size and structure, and then a charging and discharging curve test is carried out, test results can obviously show that the curves of the lithium iron phosphate lithium ion batteries prepared by the cathode pieces 1-7 prepared by the method are obviously more stable than those of a comparison group in the charging and discharging processes of the batteries, and after a plurality of times of long-term tests, the lithium iron phosphate lithium ion batteries prepared by the cathode pieces 1-7 prepared by the method have no cracks and crack growth trends.
Claims (6)
1. A preparation method of a lithium iron phosphate lithium ion battery with long service life is characterized by comprising an inner material manufacturing step, a coating step and a battery manufacturing step;
the manufacturing method of the inner material comprises the following steps: firstly, coarsely crushing petroleum coke by using a crusher, then crushing the petroleum coke in a ball mill, crushing the petroleum coke in the ball mill to a preset size, then transferring the crushed petroleum coke into a tubular furnace, heating the petroleum coke to 800-1000 ℃ in an inert gas atmosphere, preserving the heat for 1-2 hours, and then cooling the petroleum coke to room temperature to prepare a battery cathode carbon material;
in the coating step, hot water, organic alcohol and starch are prepared into a starch turbid liquid according to a preset ratio, the battery negative electrode carbon material prepared in the inner material preparation step is placed in the starch turbid liquid to be uniformly stirred and dried into powder at the temperature of 70-80 ℃ and under the inert gas atmosphere, the obtained powder is placed in a tubular furnace, the temperature is heated to 1200-1300 ℃ in the inert gas atmosphere, the temperature is kept for 1-2 hours, and then the temperature is reduced to room temperature, so that the coating of the battery negative electrode carbon material is completed;
and in the battery manufacturing step, the battery cathode carbon material processed in the coating step is used as a cathode of the lithium iron phosphate lithium ion battery to manufacture the lithium iron phosphate lithium ion battery.
2. The method of claim 1 for preparing a long life lithium iron phosphate lithium ion battery, wherein: in the inner material manufacturing step, when the coarse petroleum coke is crushed by the ball mill, the rotating speed of the ball mill is set to be 150 r/min-180 r/min.
3. The method of claim 1 or 2 for producing a long life lithium iron phosphate lithium ion battery, wherein: in the inner material manufacturing step, after the coarse broken petroleum coke is broken by the ball mill, the petroleum coke is broken into particles of 10-15 um, namely the predetermined size.
4. The method of claim 1 or 2 for producing a long life lithium iron phosphate lithium ion battery, wherein: in the inner material manufacturing step, the inert gas in the tubular furnace is nitrogen, argon or a mixed gas of two gases.
5. The method of claim 1 for preparing a long life lithium iron phosphate lithium ion battery, wherein: in the coating step, hot water, organic alcohol and starch are adopted to prepare a starch turbid liquid according to a predetermined ratio, and the method comprises the following specific steps:
firstly, preparing a starch turbid solution, wherein the preparation process comprises the steps of heating water to 60-80 ℃, continuously stirring, and slowly adding organic alcohol into the water until the concentration of the organic alcohol in the water reaches 0.1-0.2 mol/L to obtain an organic alcohol water solution;
and then slowly adding starch into the organic alcohol aqueous solution until the adding amount of the starch in the organic alcohol aqueous solution reaches 1000-1200 g/L, and continuously stirring in the process of adding the starch into the organic alcohol aqueous solution until the starch and the organic alcohol aqueous solution form uniform liquid.
6. The method of claim 1 or 6 for producing a long life lithium iron phosphate lithium ion battery, wherein: in the coating step, the organic alcohol is ethylene glycol, glycerol or a mixed liquid of two alcohols.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210532972.XA CN114899380A (en) | 2022-05-17 | 2022-05-17 | Preparation method of lithium iron phosphate lithium ion battery with long service life |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210532972.XA CN114899380A (en) | 2022-05-17 | 2022-05-17 | Preparation method of lithium iron phosphate lithium ion battery with long service life |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114899380A true CN114899380A (en) | 2022-08-12 |
Family
ID=82723855
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210532972.XA Pending CN114899380A (en) | 2022-05-17 | 2022-05-17 | Preparation method of lithium iron phosphate lithium ion battery with long service life |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114899380A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020081483A1 (en) * | 1997-07-29 | 2002-06-27 | Ngk Insulators, Ltd. | Lithium secondary battery |
| CN101492576A (en) * | 2008-01-22 | 2009-07-29 | 中国科学院化学研究所 | Carbon nano-complex particle, preparation and uses thereof |
| CN103035899A (en) * | 2013-01-14 | 2013-04-10 | 山东天润丰新能源科技有限公司 | Method for performing carbon coating modification on nano-powder by adopting water-soluble polymer |
| CN109950548A (en) * | 2019-03-29 | 2019-06-28 | 中国科学院物理研究所 | A kind of carbon composite and its preparation method and application for secondary cell |
| CN113889593A (en) * | 2020-07-02 | 2022-01-04 | 洛阳月星新能源科技有限公司 | Preparation method of hard carbon-coated soft carbon composite material |
-
2022
- 2022-05-17 CN CN202210532972.XA patent/CN114899380A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020081483A1 (en) * | 1997-07-29 | 2002-06-27 | Ngk Insulators, Ltd. | Lithium secondary battery |
| CN101492576A (en) * | 2008-01-22 | 2009-07-29 | 中国科学院化学研究所 | Carbon nano-complex particle, preparation and uses thereof |
| CN103035899A (en) * | 2013-01-14 | 2013-04-10 | 山东天润丰新能源科技有限公司 | Method for performing carbon coating modification on nano-powder by adopting water-soluble polymer |
| CN109950548A (en) * | 2019-03-29 | 2019-06-28 | 中国科学院物理研究所 | A kind of carbon composite and its preparation method and application for secondary cell |
| CN113889593A (en) * | 2020-07-02 | 2022-01-04 | 洛阳月星新能源科技有限公司 | Preparation method of hard carbon-coated soft carbon composite material |
Non-Patent Citations (1)
| Title |
|---|
| 陈壹华: "石油焦热处理过程的研究", 《轻金属》, pages 46 - 51 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113206246A (en) | Biomass hard carbon negative electrode material of sodium ion battery and preparation method thereof | |
| CN110833799B (en) | Graphene-elemental silicon composite aerogel and preparation method thereof | |
| CN113594453B (en) | Sodium-ion battery negative electrode material and preparation method thereof | |
| CN115259136A (en) | Method for preparing biomass-based hard carbon material in large batch by using waste biomass | |
| CN105140471A (en) | MoS2/C lithium-ion battery anode composite material and preparation method thereof | |
| CN115939345A (en) | Preparation method of nitrogen-doped carbon-coated modified polyanionic positive electrode material | |
| CN110931779A (en) | High-capacity long-life aqueous zinc ion battery positive electrode material and preparation method thereof | |
| CN114566727A (en) | Modification method for direct pyrogenic repair and regeneration of lithium iron phosphate positive electrode material | |
| CN115385323A (en) | Heteroatom-doped biomass-derived hard carbon negative electrode material and preparation method thereof | |
| CN113998700B (en) | Method for preparing Si/SiC@C anode material by taking micro silicon powder as raw material | |
| CN108383099B (en) | Method for preparing sodium ion battery cathode material by utilizing honeycomb | |
| CN116553524B (en) | Hard carbon negative electrode material of sodium ion battery, and preparation process and application thereof | |
| CN108539221A (en) | A kind of lithium battery production technology | |
| CN114899380A (en) | Preparation method of lithium iron phosphate lithium ion battery with long service life | |
| CN115304051B (en) | Soft carbon material containing closed pores and preparation method and application thereof | |
| CN113130887A (en) | Lithium supplementing method of lithium ion battery | |
| CN115947336A (en) | Sodium ion battery and modified hard carbon cathode thereof | |
| CN109686944A (en) | A kind of carbon coating lithium alloy combination electrode material and preparation method thereof | |
| CN115172884A (en) | Method for improving conductivity of solid electrolyte LATP ions | |
| CN109755531B (en) | Porous carbon-sulfur composite material based on acid horn shell and preparation method and application thereof | |
| CN113078295A (en) | All-solid-state zinc-sulfur battery and manufacturing method thereof | |
| CN112830483A (en) | Preparation method of high-rate graphite negative electrode material | |
| CN111533182A (en) | Solvothermal preparation method of high-lithium-ion-diffusion ternary cathode material | |
| CN112331847A (en) | Method for preparing high-electrochemical-activity lithium iron phosphate positive electrode material by using unqualified lithium iron phosphate positive electrode material | |
| CN109686975A (en) | A kind of hard charcoal negative electrode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Yin Wanshan Inventor after: Zhang Zhongwei Inventor after: He Ping Inventor before: Yang Dashuai Inventor before: Zhang Zhongwei Inventor before: Yin Wanshan Inventor before: He Ping |
|
| CB03 | Change of inventor or designer information |