CN113471425A - Preparation method of lithium ion battery - Google Patents
Preparation method of lithium ion battery Download PDFInfo
- Publication number
- CN113471425A CN113471425A CN202110616059.3A CN202110616059A CN113471425A CN 113471425 A CN113471425 A CN 113471425A CN 202110616059 A CN202110616059 A CN 202110616059A CN 113471425 A CN113471425 A CN 113471425A
- Authority
- CN
- China
- Prior art keywords
- lithium
- liznpo
- active material
- phosphoric acid
- ion battery
- 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.)
- Withdrawn
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
- H01M4/58—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- 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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a lithium ion battery. The cathode active material of the battery is LiZnPO4The anode active material is LiFePO4The electrolyte is Li2SO4‑ZnSO4The open-circuit voltage of the aqueous solution is about 1.24V, and the first charge-discharge specific capacity under the current density of 1C is 302.4mAh g‑1/261.1mAh g‑1. The water system electrolyte lithium ion battery has better electrochemical reaction activity.
Description
Technical Field
The invention relates to a lithium ion battery, in particular to a lithium ion battery taking lithium zinc phosphate as a negative active material and lithium iron phosphate as a positive active material.
Background
Lithium ion batteries have been widely used in electronic information products, but with the rapid increase of large-scale application requirements of electric vehicles, energy storage and the like, the problems of lithium ion batteries in the aspects of cost, safety, resource supply and the like are still more prominent. The commercial lithium iron phosphate battery using the lithium iron phosphate as the positive active material has the advantages of excellent cycle life, low raw material cost and relatively good safety performance, and is considered to be an ideal chemical power source for power and energy storage applications.
At present, commercial lithium iron phosphate batteries mainly adopt organic electrolytes which are inflammable, have low conductivity and high cost, have strict technical requirements and fluorine pollution, and carbon negative active materials which have the hidden danger of dendritic crystal precipitation of metallic lithium. Therefore, research and development of a novel non-traditional electrolyte lithium iron phosphate battery are necessary.
The lithium iron phosphate battery adopting the water-based electrolyte has the advantages of good rate capability, low price, relative safety, environmental protection and the like, and becomes a hotspot of research and development. At present, the main research and report on water-based lithium iron phosphate batteries is LiTi2(PO4)3|1.0MLi2SO4|LiFePO4、Zn|1MLiCl+15MZnCl2|LiFePO4、LiV3O8|9MLiNO3|C@LiFePO4And the like, wherein part of the lithium iron phosphate battery system has excellent cycle performance and high rate performance and has good application potential.
Based on the method, the novel water-system lithium iron phosphate battery with better electrochemical performance is manufactured in a trial mode.
Disclosure of Invention
The invention aims to provide a preparation method of a novel water-based lithium iron phosphate battery.
The method comprises the following specific steps:
(1) respectively taking lithium hydroxide, phosphoric acid and zinc phosphate according to the molar ratio of 3:1:1, placing the lithium hydroxide, the phosphoric acid and the zinc phosphate into an agate ball milling tank, and rotating at the speed of 1400 r.min-1The high-speed oscillating ball mill is used for grinding for 2 hours, and the ball-milled product is put in a muffle furnace at the temperature of 10 ℃ for min-1Heating to 700 ℃ at a heating rate, preserving heat for 2h, and then naturally cooling to room temperature to obtain LiZnPO4The preparation process is shown in the following chemical reaction equation:
3LiOH+H3PO4+Zn3(PO4)2＝3LiZnPO4+3H2O
(2) mixing the LiZnPO prepared in the step (1)4Mixing an active material with graphite and acetylene black according to a mass ratio of 80:5:15, grinding for half an hour, adding a proper amount of ethanol and 30 wt% of PTFE emulsion, continuously grinding to be in a nearly dry slurry state, then uniformly coating the mixture on a pre-deoiled brass mesh collector with a coating area of 1cm multiplied by 1cm and a thickness of 0.15mm, and then drying in a blast drying oven at 80 ℃ for 8 hours to obtain a lithium zinc phosphate negative plate, wherein the active material is LiZnPO4Is about 8 mg.
(3) Preparing a lithium iron phosphate positive plate with a stainless steel net as a collector by adopting the same method and steps as the step (2), wherein the active material LiFePO of the lithium iron phosphate positive plate4Is about 20 mg.
(4) 1.9MLi prepared with deionized water2SO4+0.5MZnSO4An aqueous electrolyte having a pH of about 4.2.
(5) Adopting the lithium zinc phosphate negative plate, the lithium iron phosphate positive plate and the 1.9MLi prepared in the steps (2), (3) and (4)2SO4+0.5MZnSO4And (3) assembling the water system electrolyte and the vinylon diaphragm into the laminated full cell, and standing for 0.5h to test the electrochemical performance of the laminated full cell.
(6) And (5) respectively testing the cyclic voltammetry curve and the charging and discharging curve of the water system lithium iron phosphate battery prepared in the step (5) by using an electrochemical workstation and a battery performance tester. Wherein the voltage range of the cyclic voltammetry test is 0.6V-1.8V, and the voltage scanning rate is 0.5mVs-1(ii) a The voltage range of the charge and discharge test is 0.6V-1.8V, and the current density is 1C (1C is 320 mAhg)-1)。
Drawings
Fig. 1 is an X-ray diffraction spectrum of a lithium zinc phosphate negative active material prepared in examples of the present invention.
FIG. 2 is a cyclic voltammetry curve of the water-based lithium iron phosphate battery of the embodiment of the invention at 1-10 weeks.
Fig. 3 shows the 1 st, 10 th and 100 th charge-discharge curves of the aqueous lithium iron phosphate battery according to the example of the present invention.
Detailed Description
The present invention is further described below with reference to examples.
Example (b):
(1) 2.52g of lithium hydroxide (LiOH. H) was taken in a molar ratio of 3:1:1, respectively2O, analytically pure, Guangdong Xiong chemical Co., Ltd.), and 1.03mL of phosphoric acid (H3PO485 wt%, Guangdong Xiong chemical Co., Ltd.) and zinc phosphate 8.08g (Zn)3(PO4)2·4H2O, analytically pure, Kangsu chemical Co., Ltd.) was placed in an agate jar at 1400rmin-1Grinding for 2h in a high-speed pendulum vibration ball mill (SFM-3, Lifeiki Crystal Material technology Co., Ltd.), and placing the ball-milled product in a muffle furnace (SK-2-12, Lifeiki Crystal Material Co., Ltd.) at 10 deg.C for 10min-1Heating to 700 ℃ at a heating rate, preserving heat for 2h, and then naturally cooling to room temperature to obtain LiZnPO4. X-ray diffractometer (X' Pert3Powder, Pa.Netherlands) on LiZnPO4The composition analysis was carried out, and the results are shown in FIG. 1, which is composed mainly of the product of the gamma structure and a small amount of the alpha structure.
(2) Mixing the LiZnPO prepared in the step (1)4Respectively taking 480mg, 30mg and 90mg of active material, graphite (chemical purity, Guangdong chemical industry Co., Ltd.) and acetylene black (battery grade, Guangdong chemical industry import and export Co., Ltd.) according to a mass ratio of 80:5:15, mixing the active material, the graphite, the 30mg and the acetylene black, grinding the mixture for half an hour, adding a proper amount of ethanol (analytical purity, Guangdong chemical industry Co., Ltd.) and PTFE emulsion (30 wt%, Shanghai Sanaifu new material Co., Ltd.), continuously grinding the mixture into a near dry slurry shape, uniformly coating the mixture on a collector of a pre-deoiled brass net (industrial grade, Shanghai east wire gauze Co., Ltd.), coating the collector with an area of 1cm multiplied by 1cm and a thickness of 0.15mm, and drying the collector for 8 hours in a blowing drying box (DHX-9053A, Shanghai Jing Macro apparatus Co., Ltd.) at 80 ℃ to obtain a lithium zinc phosphate negative plate, wherein the active material is LiZnPO4The payload mass of (2) is 8 mg.
(3) By adopting the same method and steps as (2), the lithium iron phosphate positive plate taking a stainless steel net (industrial grade, Oriental wire mesh company, Hebei) as a collector is prepared, and the active material LiFePO thereof4The payload mass of (2) is 20 mg.
(4) 1.9MLi prepared with deionized water2SO4+0.5MZnSO4Water systemAn electrolyte having a pH of 4.2.
(5) Adopting the lithium zinc phosphate negative plate, the lithium iron phosphate positive plate and the 1.9MLi prepared in the steps (2), (3) and (4)2SO4+0.5MZnSO4And (3) an aqueous electrolyte and a vinylon diaphragm (manufactured by Japan) are assembled into a laminated full cell, and the electrochemical performance of the laminated full cell is tested after the laminated full cell is kept still for 0.5 h.
(6) The cyclic voltammetry curve (see fig. 2) and the charge-discharge curve (see fig. 3) of the water-based lithium iron phosphate battery prepared in (5) were respectively tested by an electrochemical workstation (CHI760E, shanghai chenhua instruments ltd) and a battery performance tester (CT2001A, wuhan blue electronic devices ltd). The cyclic voltammetry curve shows that the battery has reversible charge-discharge performance, but has a cyclic performance attenuation trend; as can be seen from the charge-discharge curve, the first charge/discharge specific capacity of the battery at the current density of 1C is 297.4mAhg-1/261.1mAhg-1And the specific capacity of the 10 th charge/discharge was 93.2mAhg-1/82.0mAhg-1The 100 th charge/discharge specific capacity was 13.9mAhg-1/13.7mAhg-1。
Claims (1)
1. A preparation method of a lithium ion battery is characterized by comprising the following specific steps:
(1) respectively taking lithium hydroxide, phosphoric acid and phosphoric acid according to a molar ratio of 3:1:1, placing the lithium hydroxide, the phosphoric acid and the phosphoric acid into an agate ball milling tank, carrying out ball milling reaction for 0.5-4 h, and placing ball-milled products into a muffle furnace for 10min-1～20℃min-1Heating to 700 ℃ at a heating rate, preserving heat for 0.5-8 h, and naturally cooling to room temperature to obtain LiZnPO4A negative electrode active material;
(2) LiZnPO prepared according to claim (1)4The active material, graphite and acetylene black are mixed according to the mass ratio of (70-90): (5-10): (5-20), grinding for 10-40 min by using an agate mortar, adding a proper amount of absolute ethyl alcohol and 30% by weight of PTFE emulsion, continuously grinding to be in a nearly dry slurry state, uniformly coating on a pre-deoiled 30-to-50-mesh brass screen collector with the coating area of 1cm multiplied by 1cm and the thickness of 0.10 mm-0.20 mm, and drying for 4-16 h in a blast drying box at the temperature of 80-100 ℃ to obtain a lithium zinc phosphate cathode plate, wherein LiZnPO is used as the cathode plate4The load mass of the load is 6 mg-12 mg;
(3) the same method as in claim 2, using a stainless steel mesh of 30-50 mesh as a collector, and using commercial lithium iron phosphate to prepare a lithium iron phosphate positive electrode sheet, LiFePO thereof4The load mass is 15 mg-25 mg;
(4) preparing (0.2-2.4) MLi with deionized water2SO4+(0.2～3.0)MZnSO4An aqueous electrolyte having a pH of 3.0 to 6.5;
(5) assembling the negative electrode sheet prepared in the claim (2), the positive electrode sheet prepared in the claim (3), the aqueous electrolyte prepared in the claim (4) and a vinylon diaphragm into a laminated full cell to obtain LiZnPO4/LiFePO4A lithium ion battery;
(6) according to claim 5, the separator used is not limited to vinylon film, and any other ion-permeable film such as glass fiber film, cellulose film, or nonwoven fabric having good wettability with an aqueous electrolyte can be used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110616059.3A CN113471425A (en) | 2021-06-02 | 2021-06-02 | Preparation method of lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110616059.3A CN113471425A (en) | 2021-06-02 | 2021-06-02 | Preparation method of lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113471425A true CN113471425A (en) | 2021-10-01 |
Family
ID=77872120
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110616059.3A Withdrawn CN113471425A (en) | 2021-06-02 | 2021-06-02 | Preparation method of lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113471425A (en) |
-
2021
- 2021-06-02 CN CN202110616059.3A patent/CN113471425A/en not_active Withdrawn
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112038626A (en) | Tin-carbon composite material for lithium ion battery cathode and preparation method thereof | |
| CN110661032A (en) | Solid electrolyte film and application thereof | |
| CN110534712A (en) | A kind of black phosphorus-titanium dioxide-carbon compound cathode materials and preparation method and application | |
| CN113948764A (en) | Preparation method and application of sulfide solid electrolyte material | |
| CN110707294B (en) | Lithium-philic heteroatom and metal oxide co-doped three-dimensional fiber framework lithium battery cathode and preparation method thereof | |
| CN109037552A (en) | A kind of preparation method of the diaphragm material for sodium-sulphur battery | |
| CN107732221A (en) | A kind of stable compound lithium ion battery negative material α Ga2O3 and preparation method | |
| CN116130782A (en) | Method for preparing lithium ion battery and application | |
| CN111313010A (en) | Preparation method of high-capacity lithium ion battery anode material lithium iron phosphate | |
| CN115679380A (en) | Preparation method and application of crystal face oriented metal zinc | |
| CN104993131B (en) | A kind of lithium ion battery negative material NiS/Ni and preparation method thereof | |
| CN114613980A (en) | Zinc ion battery composite negative electrode and preparation method and application thereof | |
| CN108075131B (en) | Based on NayNixMn1-xO2Water system energy storage battery with positive electrode of sodium-rich layered compound | |
| CN113067029A (en) | Gel electrolyte 3D printing paste and forming method thereof | |
| CN115010941B (en) | Preparation method and application of ionic covalent organic framework nano-sheet protective layer through electrodeposition | |
| CN114583137B (en) | Method for modifying carbon surface by sulfur doped phosphorus and application thereof | |
| CN110707285A (en) | SnO (stannic oxide)2Negative electrode material lithium battery and positive plate thereof | |
| CN113078295B (en) | All-solid-state zinc-sulfur battery and manufacturing method thereof | |
| CN113471425A (en) | Preparation method of lithium ion battery | |
| CN111341980B (en) | Sodium perfluorosulfonate ion battery electrolyte membrane and preparation method and application thereof | |
| CN108963388A (en) | A kind of method improving lithium-air battery energy density and output power and the lithium-air battery based on this method | |
| CN108598393B (en) | Lithium ion battery anode material and preparation method thereof | |
| CN112467131A (en) | Preparation method of magnesium ion battery negative electrode material | |
| CN116779841A (en) | Solid sodium ion battery | |
| CN113422014A (en) | Polyaniline-coated tin dioxide composite 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 | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20211001 |