CN115716660A - Composite ternary metal oxide oxygen carrier material and preparation method and application thereof - Google Patents
Composite ternary metal oxide oxygen carrier material and preparation method and application thereof Download PDFInfo
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- CN115716660A CN115716660A CN202211258395.6A CN202211258395A CN115716660A CN 115716660 A CN115716660 A CN 115716660A CN 202211258395 A CN202211258395 A CN 202211258395A CN 115716660 A CN115716660 A CN 115716660A
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention discloses a composite ternary metal oxide oxygen carrier material and a preparation method and application thereof, belonging to the technical field of waste lithium battery recycling and chemical chain oxygen carrier preparation. The waste ternary lithium battery is subjected to the processes of discharging, disassembling the anode, separating the anode material from the aluminum foil, roasting at high temperature and the like in sequence to obtain NiCoMnO x The complex ternary metal oxide of (1). The method has simple operation process, recycles the waste ternary lithium battery and prepares NiCoMnO x The composite ternary metal oxide can be used as an oxygen carrier in a chemical chain process, can assist fuel conversion, and has an excellent application prospect.
Description
Technical Field
The invention relates to the technical field of waste lithium battery recycling, in particular to a composite ternary metal oxide oxygen carrier material and a preparation method and application thereof.
Background
With the further increase of the demand of electric automobiles, the ternary lithium battery will meet a new increasing demand. However, after 3-5 years of use, a large number of waste ternary lithium batteries are produced, and harmful substances in the waste ternary lithium batteries can have negative effects on ecological environment and biological health if the waste ternary lithium batteries are not treated properly. Therefore, safe recovery and green disposal are still key links for the development of the lithium battery industry.
Chemical looping combustion and reforming are novel fuel conversion technologies, have excellent characteristics of carbon dioxide capture, fuel value increment and the like, and have strong application potential. Oxygen carriers are used as media for oxygen transfer and heat transfer, and are key to chemical looping combustion and reforming technology. NiO and Co 3 O 4 、MnO 2 The transition metal oxides have good oxidation-reduction performance and lattice oxygen transfer performance, and are widely used in chemical chain combustion and reforming processes.
The ternary lithium battery anode material contains a large amount of Ni, co and Mn elements, so if transition metal elements in the waste ternary lithium battery anode material are used for preparing the composite oxide type chemical chain oxygen carrier, the environment and economic benefits of the waste ternary lithium battery can be better in resource utilization, chemical chain combustion and reforming fuel conversion.
Disclosure of Invention
The invention aims to provide a composite ternary metal oxide oxygen carrier material prepared by utilizing a waste ternary lithium battery anode and a preparation method and application thereof aiming at the defects of the prior art x The composite ternary metal oxide of (2) is used as an oxygen carrier in a chemical chain process.
In order to solve the technical problems, the invention provides the following technical scheme:
the preparation method of the composite ternary metal oxide oxygen carrier material is characterized by comprising the following steps of:
step 1: respectively connecting the positive electrode and the negative electrode of the waste ternary lithium battery into saline water, and carrying out complete discharge treatment;
step 2: disassembling the completely discharged battery, separating the positive electrode and the negative electrode in the completely discharged battery, and collecting a positive plate;
and step 3: soaking the positive plate in a citric acid aqueous solution, and carrying out ultrasonic oscillation to separate a positive active substance on the positive plate;
and 4, step 4: collecting the separated positive active substances and calcining at high temperature to obtain the composite ternary metal oxide oxygen carrier material NiCoMnO x 。
Furthermore, the chemical formula of the positive active material of the ternary lithium battery is LiNi x Co y Mn 1-x-y O 2 。
Further, the high-temperature calcination is carried out at 700-900 ℃ for 0.5-1.5h.
Further, the concentration of the citric acid aqueous solution is 0.5-1mol/L.
Further, the ultrasonic oscillation time is 20-60min.
A composite ternary metal oxide oxygen carrier material prepared by the preparation method.
The application of the composite ternary metal oxide oxygen carrier material in chemical chain combustion.
Compared with the prior art, the invention has the beneficial effects that: the method does not need to use a chemical process to dissolve the metal-based solid in the electrode material in the process of recycling the transition metal elements of Ni, co and Mn in the anode material of the waste ternary lithium battery, has simple operation process, and prepares the NiCoMnO x The composite ternary metal oxide can be used as an oxygen carrier in a chemical chain process, can assist in fuel conversion, and has an excellent application prospect.
Drawings
FIG. 1 shows NiCoMnO in examples x A surface topography of the composite ternary metal oxide oxygen carrier.
FIG. 2 shows NiCoMnO in the examples x The content of the composite ternary metal oxide oxygen carrier is 4 percent 2 Mass change rate curve in oxygen transfer process under Ar-air atmosphere.
FIG. 3 shows NiCoMnO in the examples x The content of the composite ternary metal oxide oxygen carrier is 4 percent 2 Mass change rate curve in 30 cycles under Ar-air atmosphere.
FIG. 4 shows NiCoMnO in the examples x The content of the composite ternary metal oxide oxygen carrier is 4 percent 2 In an Ar-air atmosphere for 30 timesThe change curve of the relationship between the oxygen transport capacity and the cycle times in the cycle process.
FIG. 5 shows NiCoMnO in examples x The content of the composite ternary metal oxide oxygen carrier is 20 percent CH 4 /N 2 Real-time gaseous product distribution curves under atmosphere.
Detailed Description
For the understanding of the present invention, the following detailed description of the present invention is given with reference to the accompanying drawings, which are provided for illustration purposes only and are not intended to limit the scope of the present invention.
An embodiment of a preparation method of a composite ternary metal oxide oxygen carrier material comprises the following steps:
the anode active material component of the waste ternary lithium battery used in the preparation process is LiNi x Co y Mn 1-x-y O 2 Including LiNi according to the difference of three element components 0.33 Co 0.33 Mn 0.33 O 2 (NCM333)、LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622)、LiNi 0.5 Co 0.2 Mn 0.3 O 2 (NCM523)、LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM 811) and the like, and LiNi is used in the present example 0.6 Co 0.2 Mn 0.2 O 2 (NCM622)。
Step 1: respectively connecting the positive electrode and the negative electrode of the waste ternary lithium battery into saline water, carrying out complete discharge treatment, and placing the battery for later use after complete discharge;
step 2: mechanically disassembling the completely discharged battery, breaking the shell, separating the positive electrode and the negative electrode, and collecting a positive plate;
and 3, step 3: soaking the positive plate in 1mol/L citric acid aqueous solution, and ultrasonically oscillating for 30min to separate the positive active substance on the positive plate from the aluminum foil;
and 4, step 4: collecting the separated positive active substances, and calcining at 800 ℃ for 1h to obtain the composite ternary metal oxide oxygen carrier material NiCoMnO x 。
The ternary metal oxide prepared by the embodiment can be used as an oxygen carrier material in chemical chain combustion and reforming processes.
In the aspect of chemical looping combustion, oxygen carriers react with conventional fuels to generate flue gas rich in carbon dioxide and water, the oxygen carriers are reduced, the flue gas is condensed to remove water, then the water and the carbon dioxide can be separated, the purpose of capturing the carbon dioxide is achieved, and the reduced oxygen carriers are oxidized by air to be regenerated and recycled. Evaluation indexes of the chemical looping combustion process are oxygen transport capacity and cycle stability. Oxygen transport capacity calculation formula is X =1-m f /m i Wherein m is i Denotes the initial mass of oxygen carrier per cycle, m f Indicating the mass of the oxygen carrier after it has been reduced.
In the aspect of chemical chain reforming, an oxygen carrier reacts with methane to generate synthesis gas containing hydrogen and carbon monoxide, the synthesis gas can be used as a raw material of a Fischer-Tropsch synthesis process and the like, meanwhile, the oxygen carrier is reduced, and then the reduced oxygen carrier is oxidized by air to be regenerated and recycled. The evaluation indexes of the chemical chain reforming process are CO selectivity and H 2 the/CO molar ratio. The CO selectivity calculation formula was S = C (CO)/(c (CO) 2 ) + C (CO)), wherein C (CO) 2 ) And C (CO) represents CO in the product gas 2 And the concentration of CO. H 2 Molar ratio of CO is calculated as H 2 /CO＝c(H 2 ) C (CO)), wherein c (H) 2 ) And C (CO) represents H in the product gas 2 To the concentration of CO.
NiCoMnO x And (3) measuring the oxygen transport capacity of the composite ternary metal oxide oxygen carrier:
15mg of NiCoMnO prepared by the method of the above example x The oxygen transport capacity of the composite ternary metal oxide oxygen carrier is determined on a thermogravimetric analyzer, the test temperature is 800 ℃, the reaction atmosphere is 4% 2 and/Ar. As can be seen from FIG. 2, the quality of the prepared oxygen carrier is reduced by 16% within 15min, namely the oxygen transport capacity is 0.16.
NiCoMnO x And (3) testing the cycling stability of the composite ternary metal oxide oxygen carrier:
15mg of NiCoMnO prepared by the method of the above example x Composite ternary metal oxide oxygen carrier in the presence of heatPerforming reduction-oxidation cycle stability test on the re-analyzer at 800 deg.C under a reduction reaction atmosphere of 4% 2 Ar, the oxidation reaction atmosphere is air, the reduction reaction time and the oxidation reaction time are both 15min, and N is used between the reduction reaction and the oxidation reaction 2 Purging for 5min.
As can be seen from fig. 3, the cycle stability gradually decreased during the first 15 cycles, and the cycle remained stable after the 15 th cycle, and as can be seen from fig. 4, the oxygen transport capacity was maintained at a level of 0.08 from the 15 th to 30 th cycles, and the oxygen transport capacity at the 30 th cycle was attenuated to 94.0% of that at the 15 th cycle.
NiCoMnO x The application of the composite ternary metal oxide oxygen carrier in preparing synthesis gas by chemical chain methane conversion comprises the following steps:
0.35g of NiCoMnO prepared by the method of the above example x Placing the composite ternary metal oxide oxygen carrier in a quartz tube with an inner diameter of 9mm, reacting at 800 deg.C under a reaction atmosphere of 20% 4 /N 2 。
As can be seen from FIG. 5, the methane concentration decreased and the carbon monoxide and hydrogen concentrations increased within 4.5 to 7min, indicating NiCoMnO x The composite ternary metal oxide oxygen carrier can be applied to the process of preparing synthesis gas by chemical chain methane conversion. Wherein, the real-time H is within 4.7-5.2 min 2 The molar ratio of/CO is slightly higher than 2, during which H 2 The average value of the mol ratio of/CO is 2.33, the average value of the selectivity of CO is 75.6 percent, and the values are close to the values reported in the prior literature.
The above embodiments are merely illustrative of the technical concept and structural features of the present invention, and are intended to be implemented by those skilled in the art, but the present invention is not limited thereto, and any equivalent changes or modifications made according to the spirit of the present invention should fall within the scope of the present invention.
Claims (7)
1. The preparation method of the composite ternary metal oxide oxygen carrier material is characterized by comprising the following steps of:
step 1: respectively connecting the positive electrode and the negative electrode of the waste ternary lithium battery into saline water, and carrying out complete discharge treatment;
and 2, step: disassembling the completely discharged battery, separating the positive electrode and the negative electrode in the completely discharged battery, and collecting a positive plate;
and step 3: soaking the positive plate in a citric acid aqueous solution, and carrying out ultrasonic oscillation to separate a positive active substance on the positive plate;
and 4, step 4: collecting and calcining the separated positive active substances to obtain the composite ternary metal oxide oxygen carrier material NiCoMnO x 。
2. The method for preparing the composite ternary metal oxide oxygen carrier material according to claim 1, wherein the method comprises the following steps: the chemical formula of the positive active material component of the ternary lithium battery is LiNi x Co y Mn 1-x-y O 2 。
3. The method for preparing the composite ternary metal oxide oxygen carrier material according to claim 1, wherein the method comprises the following steps: the high-temperature calcination is carried out at the temperature of 700-900 ℃ for 0.5-1.5h.
4. The method for preparing the composite ternary metal oxide oxygen carrier material according to claim 1, wherein the method comprises the following steps: the concentration of the citric acid aqueous solution is 0.5-1mol/L.
5. The preparation method of the composite ternary metal oxide oxygen carrier material according to claim 1, characterized in that: the ultrasonic oscillation time is 20-60min.
6. A composite ternary metal oxide oxygen carrier material prepared by the preparation method according to any one of claims 1 to 5.
7. Use of the composite ternary metal oxide oxygen carrier material according to claim 6 in chemical looping combustion and reforming.
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Citations (5)
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| CN103387865A (en) * | 2012-05-10 | 2013-11-13 | 清华大学 | High-performance double-core iron-based oxygen carrier particle and preparation method thereof |
| CN104130821A (en) * | 2014-08-07 | 2014-11-05 | 南京理工大学 | Manganese-containing cobalt-based complex oxygen carrier and preparation method thereof |
| CN108285977A (en) * | 2018-01-30 | 2018-07-17 | 武汉科技大学 | A kind of method of waste lithium ion cell anode material recovery |
| CN108767351A (en) * | 2018-04-19 | 2018-11-06 | 江苏理工学院 | A kind of regeneration method of waste and old nickel-cobalt-manganese ternary anode material of lithium battery |
| CN113713828A (en) * | 2021-09-16 | 2021-11-30 | 中国科学院大学 | VOCs combustion catalyst prepared by recycling waste ternary lithium batteries and preparation method thereof |
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- 2022-10-14 CN CN202211258395.6A patent/CN115716660A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103387865A (en) * | 2012-05-10 | 2013-11-13 | 清华大学 | High-performance double-core iron-based oxygen carrier particle and preparation method thereof |
| CN104130821A (en) * | 2014-08-07 | 2014-11-05 | 南京理工大学 | Manganese-containing cobalt-based complex oxygen carrier and preparation method thereof |
| CN108285977A (en) * | 2018-01-30 | 2018-07-17 | 武汉科技大学 | A kind of method of waste lithium ion cell anode material recovery |
| CN108767351A (en) * | 2018-04-19 | 2018-11-06 | 江苏理工学院 | A kind of regeneration method of waste and old nickel-cobalt-manganese ternary anode material of lithium battery |
| CN113713828A (en) * | 2021-09-16 | 2021-11-30 | 中国科学院大学 | VOCs combustion catalyst prepared by recycling waste ternary lithium batteries and preparation method thereof |
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