CN113964405A - Method for monitoring surface residual alkali concentration of high-voltage lithium cobalt oxide on line - Google Patents
Method for monitoring surface residual alkali concentration of high-voltage lithium cobalt oxide on line Download PDFInfo
- Publication number
- CN113964405A CN113964405A CN202111180961.1A CN202111180961A CN113964405A CN 113964405 A CN113964405 A CN 113964405A CN 202111180961 A CN202111180961 A CN 202111180961A CN 113964405 A CN113964405 A CN 113964405A
- Authority
- CN
- China
- Prior art keywords
- sintering kiln
- concentration
- residual alkali
- sintering
- kiln
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
- H01M10/484—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte for measuring electrolyte level, electrolyte density or electrolyte conductivity
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/12—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using combustion
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/52—Removing gases inside the secondary cell, e.g. by absorption
-
- 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 method for monitoring the concentration of residual alkali on the surface of high-voltage lithium cobaltate on line, which comprises the following steps: setting a temperature curve and air intake and exhaust volume of a sintering kiln, and after the set parameters are reached and stabilized, putting materials into the sintering kiln for sintering; determination of CO in various temperature zones in a sintering kiln2Concentration, gas flow rate of each exhaust pipe; testing the residual alkali content on the surface of the sintered product; repeating for multiple times as basic data; analysis of CO in each temperature zone2Concentration data, determining gas flow direction and CO in the sintering kiln2A distribution state; analyzing gas flow data of each exhaust pipe; increasing the air inflow of the area with the highest solid phase reaction activity, wrapping the exhaust pipe of the area by refractory cotton, and changing the exhaust pipe of the area into direct exhaust; testing CO in sintering kiln2Concentration, simultaneously sampling the sintered product for testing surface residual alkaliContent and analyze the data. The invention can obviously reduce the residual alkali on the surface of the discharged furnace material, improve the stability of the high-voltage lithium cobalt oxide material and reduce the gas expansion of the lithium cobalt oxide battery.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a method for monitoring the concentration of residual alkali on the surface of high-voltage lithium cobalt oxide on line.
Background
With the rapid development of new energy markets, people put higher requirements on the energy density of lithium ion batteries, and lithium cobaltate materials as the first generation anode materials of the lithium ion batteries have wide application prospects in the fields of communication, consumer electronics, computers and the like. Along with the development of the market, people put forward higher and higher requirements on indexes such as capacity and cycle performance of a lithium cobaltate material, and the high-voltage lithium cobaltate is modified by means of trace doping of various elements so as to improve the stability of the high-voltage lithium cobaltate in the high-voltage charging and discharging process.
In the process of synthesizing high-voltage lithium cobalt oxide, adverse characteristics such as high residual alkali degree on the surface of the material can be displayed, so that the structure of the material is damaged in the process of inserting and removing lithium ions, certain gas and heat are generated, and the safety performance of a lithium ion battery is influenced. Improve this problem of lithium cobaltate material surface residual alkalinity too high at present, on the one hand through weighing at compounding in-process accuracy, control lithium carbonate use amount, on the other hand is in sintering process, accurate regulation and control sintering atmosphere cooperates section temperature setting and accurate filling control simultaneously, the reaction rate of material in the sagger is improved to moulding-die control, make the material in the sagger fully contact with external oxygen, the carbon dioxide and the moisture of production can be taken away more fast, thereby can effectively reduce out furnace charge surface residual alkali content.
Disclosure of Invention
Aiming at the problem of overhigh surface residual alkali of the high-voltage lithium cobalt oxide positive electrode material in the prior art, the invention provides the method for monitoring the surface residual alkali concentration of the high-voltage lithium cobalt oxide on line, which can obviously reduce the surface residual alkali of the discharged furnace material, improve the stability of the high-voltage lithium cobalt oxide material and reduce the gas expansion of a lithium cobalt oxide battery.
The invention adopts the following technical scheme:
a method for monitoring the concentration of residual alkali on the surface of high-voltage lithium cobaltate on line is characterized by comprising the following steps:
(1) setting a temperature curve and air intake and exhaust amount of the sintering kiln, and when the sintering kiln reaches set parameters and is stable, putting materials into the sintering kiln, and continuously sintering the materials;
(2) continuously feeding materials into a sintering kiln to obtain a sintered product, and measuring CO in each temperature zone in the sintering kiln2Concentration; measuring the gas flow of each exhaust pipe of the sintering kiln; sampling the sintered product to test the content of residual alkali on the surface; repeating the step (2) for multiple times to serve as basic data;
(3) analysis of CO in various temperature zones in a sintering kiln2Concentration data, determining gas flow direction and CO in the sintering kiln2The distribution state is determined, and the area with the highest solid phase reaction activity is determined;
(4) analyzing gas flow data of each exhaust pipe of the sintering kiln, and confirming the exhaust condition of the region with the highest solid-phase reaction activity;
(5) the region with the highest solid phase reactivity is increased by O2An air intake amount; wrapping the exhaust pipe in the area with the highest solid phase reaction activity by refractory cotton, and directly exhausting the exhaust pipe in the area with the highest solid phase reaction activity;
(6) testing CO in sintering kiln2And (5) simultaneously sampling the sintered product to test the content of residual alkali on the surface and analyzing the data.
According to the method for monitoring the concentration of the residual alkali on the surface of the high-voltage lithium cobaltate on line, the sintering kiln is an air kiln.
The method for monitoring the concentration of the residual alkali on the surface of the high-voltage lithium cobaltate on line is characterized in that in the step (1), a temperature curve and air intake and exhaust volume of a sintering kiln are set according to a sintering process, and when the sintering kiln is stabilized for 24-36 hours after reaching set parameters, materials are put into the sintering kiln and are continuously sintered.
The method for monitoring the concentration of the residual alkali on the surface of the high-voltage lithium cobaltate on line is characterized in that in the step (2), the materials are continuously fed into the sintering kiln for 24-72 hours, and then a sintered product is obtained.
The method for monitoring the concentration of the residual alkali on the surface of the high-voltage lithium cobaltate on line is characterized in that the step (2) is repeated 7 to 15 times as basic data.
The method for monitoring the concentration of the residual alkali on the surface of the high-voltage lithium cobaltate on line is characterized in that the CO in the sintering kiln is tested after 24-48 hours in the step (6)2And (5) simultaneously sampling the sintered product to test the content of residual alkali on the surface and analyzing the data.
The invention has the beneficial technical effects that: the invention analyzes CO2And data, analyzing the reactivity of materials in each area in the kiln, determining the area with high reactivity, and adjusting the sintering atmosphere by changing the exhaust of the area with high reactivity into direct exhaust, so that the content of residual alkali on the surface of the high-voltage lithium cobalt oxide material is reduced, the accurate control of the production process is realized, and the performance of the product is improved. The method provided by the invention is simple and practical, and the sintering atmosphere is adjusted by changing bell mouth air suction into direct air exhaust, so that the exhaust of waste gas is accelerated, the reaction rate of solid-phase reaction is improved, the performance of sintering equipment is improved, stable support is provided for improving the performance of products, the residual alkali on the surface of discharged materials is obviously reduced, the stability of high-voltage lithium cobaltate materials is improved, and the gas expansion performance of lithium cobaltate batteries is reduced.
Drawings
FIG. 1 shows CO in example 12Concentration data analysis chart.
Detailed Description
The invention discloses a method for monitoring the concentration of residual alkali on the surface of high-voltage lithium cobaltate on line, which comprises the following steps:
(1) setting the temperature curve and the air intake and exhaust amount of the sintering kiln according to the sintering process, and when the sintering kiln is stabilized for 24-36 hours after reaching set parameters, adding materials into the sintering kiln, and continuously sintering the materials. The sintering kiln is an air kiln.
(2) Counter heatingContinuously adding materials into the sintering kiln for 24-72 hours to obtain a sintered product, and measuring CO in each temperature zone in the sintering kiln2Concentration; because the kiln is an air kiln, the sealing performance is poor, and the furnace pressure test is difficult, the concentration of CO2 is approximate to the furnace pressure. Measuring the gas flow of each exhaust pipe of the sintering kiln; sampling the sintered product to test the content of residual alkali on the surface; repeating the step (2) for 7-15 times as basic data.
(3) Analyzing CO in each temperature zone in the sintering kiln in the step (2)2Concentration data, determining gas flow direction and CO in the sintering kiln2And (4) distribution state, thereby determining the region with the highest solid phase reactivity.
(4) And (3) analyzing the gas flow data of each exhaust pipe of the sintering kiln in the step (2) and confirming the exhaust condition of the region with the highest solid-phase reaction activity.
(5) Adjusting air inlet setting: increasing the area with the highest solid phase reaction activity in the step (3) to be O2Air intake quantity, providing sufficient O2So as to facilitate the reaction; adjusting exhaust, wrapping the exhaust pipe in the area with highest solid phase reaction activity in the step (3) with refractory cotton, directly exhausting the exhaust pipe in the area with highest solid phase reaction activity, increasing the exhaust amount, and generating CO by reaction2And is discharged as soon as possible.
(6) Testing CO in the sintering kiln after 24-48 hours2And (4) simultaneously sampling the sintered product to test the residual alkali content on the surface, analyzing data, and judging whether the modified air inlet and exhaust settings reach expectations or not.
Example 1
(1) Collecting kiln CO for 7 days2And taking the data, the exhaust pipe flow data and the residual alkali data on the surface of the sintered product as basic data, and analyzing the data.
(2) Analysis of the underlying data for CO discovery2Concentration peaks are concentrated in the 6-11 region and the 16-20 region, and the high reaction activity region is judged to be CO in the 6-11 region and the 16-20 region2The concentration peak is likely to have larger air inflow with the temperature rising section, and CO generated in the temperature rising section due to the pressure gradient is formed2Flowing to the region; the adjustment measures are as follows: the exhaust gas in the 7-12 areas is changed into a straight exhaust gas.
(3) After 24 hoursTesting of CO2Concentration, first CO was found2Narrowing of the concentration peak, second CO2The concentration peak is not changed, and the adjustment measures are as follows: the air inflow in the 9-15 areas is from 40m3The adjustment of the reaction time/h is 35m3And h, adjusting the frequency of the furnace end exhaust fan from 40Hz to 42 Hz.
(4) Testing CO after 24 hours2Concentration, found in region 6-11, shifted to region 8-12, with a second CO2No significant change in the concentration peaks indicates that the first CO is amplified by the exhaust2The concentration peaks have an influence.
(5) After the test result is analyzed, the adjustment measures are provided as follows: the flow rate of the inlet air in the 20-26 areas is 10m3The adjustment of the reaction time/h is 15m3H, increasing the furnace pressure in the constant temperature zone to supply a second CO2The concentration peak is pushed to the temperature rising section to promote the forward movement of the concentration peak.
(6) Testing CO after 24 hours2Concentration, analysis of data reveals a second CO2The concentration peak is not obviously changed, which indicates that the method for increasing the furnace pressure of the constant temperature section is not effective, the frequency of a large induced draft fan on the roof is determined to be increased (adjusted from 30Hz to 35Hz), and the scheduling speed is increased to reduce the whole CO2And (4) concentration.
(7) Testing CO again after 24 hours2Concentration, analysis of data to find CO2Bimodal, but CO still exists2The level is reduced by 500-700ppm compared with that before adjustment, which shows that the improvement of exhaust gas achieves the reduction of CO2The concentration effect, and the surface residual alkali content of the product is reduced to about 1500ppm from the previous 2500 ppm. Table 1 shows the surface residual alkali content of the high voltage lithium cobaltate in example 1. FIG. 1 shows CO in example 12And (6) analyzing concentration data.
TABLE 1 content of residual alkali on the surface of high-voltage lithium cobalt oxide
Claims (6)
1. A method for monitoring the concentration of residual alkali on the surface of high-voltage lithium cobaltate on line is characterized by comprising the following steps:
(1) setting a temperature curve and air intake and exhaust amount of the sintering kiln, and when the sintering kiln reaches set parameters and is stable, putting materials into the sintering kiln, and continuously sintering the materials;
(2) continuously feeding materials into a sintering kiln to obtain a sintered product, and measuring CO in each temperature zone in the sintering kiln2Concentration; measuring the gas flow of each exhaust pipe of the sintering kiln; sampling the sintered product to test the content of residual alkali on the surface; repeating the step (2) for multiple times to serve as basic data;
(3) analysis of CO in various temperature zones in a sintering kiln2Concentration data, determining gas flow direction and CO in the sintering kiln2The distribution state is determined, and the area with the highest solid phase reaction activity is determined;
(4) analyzing gas flow data of each exhaust pipe of the sintering kiln, and confirming the exhaust condition of the region with the highest solid-phase reaction activity;
(5) the region with the highest solid phase reactivity is increased by O2An air intake amount; wrapping the exhaust pipe in the area with the highest solid phase reaction activity by refractory cotton, and directly exhausting the exhaust pipe in the area with the highest solid phase reaction activity;
(6) testing CO in sintering kiln2And (5) simultaneously sampling the sintered product to test the content of residual alkali on the surface and analyzing the data.
2. The method of on-line monitoring of the concentration of residual alkali on the surface of high voltage lithium cobaltate according to claim 1, wherein the sintering kiln is an air kiln.
3. The method for monitoring the concentration of the residual alkali on the surface of the high-voltage lithium cobaltate on line according to the claim 1, wherein the temperature curve and the air intake and exhaust amount of the sintering kiln are set according to the sintering process in the step (1), and when the sintering kiln is stabilized for 24-36 hours after reaching the set parameters, the materials are put into the sintering kiln, and the materials are continuously sintered.
4. The method for monitoring the surface residual alkali concentration of the high-voltage lithium cobaltate on line according to claim 1, wherein the sintered product is obtained after the materials are continuously fed into the sintering kiln for 24-72 hours in the step (2).
5. The method for on-line monitoring the surface residual alkali concentration of high-voltage lithium cobaltate according to claim 4, wherein the step (2) is repeated 7-15 times as basic data.
6. The method for on-line monitoring of the surface residual alkali concentration of high-voltage lithium cobaltate according to claim 4, wherein the CO in the sintering kiln is tested in step (6) after 24-48 hours2And (5) simultaneously sampling the sintered product to test the content of residual alkali on the surface and analyzing the data.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111180961.1A CN113964405A (en) | 2021-10-11 | 2021-10-11 | Method for monitoring surface residual alkali concentration of high-voltage lithium cobalt oxide on line |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111180961.1A CN113964405A (en) | 2021-10-11 | 2021-10-11 | Method for monitoring surface residual alkali concentration of high-voltage lithium cobalt oxide on line |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113964405A true CN113964405A (en) | 2022-01-21 |
Family
ID=79463901
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111180961.1A Pending CN113964405A (en) | 2021-10-11 | 2021-10-11 | Method for monitoring surface residual alkali concentration of high-voltage lithium cobalt oxide on line |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113964405A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115792095A (en) * | 2023-02-01 | 2023-03-14 | 山东海科创新研究院有限公司 | Non-aqueous detection method for surface residual alkali of positive active material and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104229838A (en) * | 2014-09-23 | 2014-12-24 | 中国科学院青海盐湖研究所 | Method for improving carbonization efficiency of lithium carbonate by controlling gas flow |
| CN106970542A (en) * | 2017-03-27 | 2017-07-21 | 合肥瑞石测控工程技术有限公司 | One kind visualization pyrolysis furnace charring state monitoring apparatus |
| JP2018008913A (en) * | 2016-07-15 | 2018-01-18 | 富士通株式会社 | Monitoring method, monitoring device, monitoring program, and power generation system |
| CN108956850A (en) * | 2017-05-17 | 2018-12-07 | 北大先行科技产业有限公司 | A kind of detection method of Fast Evaluation tertiary cathode material surface residual alkali relative amount |
| CN211176804U (en) * | 2019-08-27 | 2020-08-04 | 光大环保技术装备（常州）有限公司 | Plasma melting furnace and air supply device thereof |
-
2021
- 2021-10-11 CN CN202111180961.1A patent/CN113964405A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104229838A (en) * | 2014-09-23 | 2014-12-24 | 中国科学院青海盐湖研究所 | Method for improving carbonization efficiency of lithium carbonate by controlling gas flow |
| JP2018008913A (en) * | 2016-07-15 | 2018-01-18 | 富士通株式会社 | Monitoring method, monitoring device, monitoring program, and power generation system |
| CN106970542A (en) * | 2017-03-27 | 2017-07-21 | 合肥瑞石测控工程技术有限公司 | One kind visualization pyrolysis furnace charring state monitoring apparatus |
| CN108956850A (en) * | 2017-05-17 | 2018-12-07 | 北大先行科技产业有限公司 | A kind of detection method of Fast Evaluation tertiary cathode material surface residual alkali relative amount |
| CN211176804U (en) * | 2019-08-27 | 2020-08-04 | 光大环保技术装备（常州）有限公司 | Plasma melting furnace and air supply device thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115792095A (en) * | 2023-02-01 | 2023-03-14 | 山东海科创新研究院有限公司 | Non-aqueous detection method for surface residual alkali of positive active material and application |
| CN115792095B (en) * | 2023-02-01 | 2023-06-27 | 山东海科创新研究院有限公司 | Nonaqueous detection method for residual alkali on surface of positive electrode active material and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110501382B (en) | Measuring device and method for heat production-gas production combination of lithium ion battery | |
| CN113964405A (en) | Method for monitoring surface residual alkali concentration of high-voltage lithium cobalt oxide on line | |
| CN104979541B (en) | A kind of lithium titanate composite material and preparation method thereof | |
| CN108199062A (en) | A kind of fuel cell feed air temperature control system and method | |
| CN105091590B (en) | Sintering main exhaust fan intelligent power saving method and system | |
| CN212255614U (en) | Lithium ion battery charging lithium-separating real-time detection system | |
| CN111241715B (en) | Method for determining test parameters of pulverized coal injection combustion rate of blast furnace under different coal ratios | |
| CN110702556A (en) | Method for detecting content of silicon-based material in silicon-containing negative plate of lithium ion battery | |
| CN108956850A (en) | A kind of detection method of Fast Evaluation tertiary cathode material surface residual alkali relative amount | |
| CN104934593B (en) | A kind of microwave sintering prepares LiNi1/3Co1/3Mn1/3O2The method of material | |
| CN106356566B (en) | A kind of lithium battery and preparation method thereof | |
| CN103031435A (en) | Control method and system for sintering end point position | |
| CN104865367A (en) | Dry quenching coke burn-out rate real-time measurement method | |
| CN1156928C (en) | Active positive-pole material for lithium ion secondary cell and its preparation and use | |
| CN107797965A (en) | A kind of update method and system of pulverizer outlet temperature secure setting | |
| RU2606680C2 (en) | Method and system for controlling the main exhaust fan | |
| CN112251610A (en) | Titanium carbide slag and smelting method thereof | |
| CN114577867B (en) | Method for detecting Chang Liangji g capacity of fluorocarbon material | |
| CN108344730A (en) | The assay method of trace impurity content in a kind of high-concentration sulfuric acid vanadyl solution | |
| CN203728581U (en) | Lithium iron phosphate preparation device | |
| CN108195880A (en) | The detection method of nitrogen content in U-Gd-Zr pellets | |
| CN216525709U (en) | Raw material reaction activity testing system suitable for lithium battery anode material and lithium battery anode material production system | |
| CN113621793B (en) | Sintered solid fuel size fraction control method | |
| CN105655575A (en) | Lithium-ion battery cathode material and preparation method thereof | |
| CN216206644U (en) | Real-time monitoring system for steelmaking flue gas of electric furnace |
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 |