CN114005974A - Silica anode material, preparation method of silica anode material and lithium ion battery - Google Patents
Silica anode material, preparation method of silica anode material and lithium ion battery Download PDFInfo
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- CN114005974A CN114005974A CN202111635820.4A CN202111635820A CN114005974A CN 114005974 A CN114005974 A CN 114005974A CN 202111635820 A CN202111635820 A CN 202111635820A CN 114005974 A CN114005974 A CN 114005974A
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- silicon
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- oxygen
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 64
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000010405 anode material Substances 0.000 title claims description 33
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims abstract description 77
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 45
- 239000007773 negative electrode material Substances 0.000 claims abstract description 39
- 239000010406 cathode material Substances 0.000 claims abstract description 32
- 239000010410 layer Substances 0.000 claims abstract description 32
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 19
- 239000011247 coating layer Substances 0.000 claims abstract description 16
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 12
- 230000004048 modification Effects 0.000 claims abstract description 11
- 238000012986 modification Methods 0.000 claims abstract description 11
- WVMPCBWWBLZKPD-UHFFFAOYSA-N dilithium oxido-[oxido(oxo)silyl]oxy-oxosilane Chemical group [Li+].[Li+].[O-][Si](=O)O[Si]([O-])=O WVMPCBWWBLZKPD-UHFFFAOYSA-N 0.000 claims abstract description 10
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 61
- 238000010438 heat treatment Methods 0.000 claims description 44
- 229910052744 lithium Inorganic materials 0.000 claims description 33
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 19
- 238000000576 coating method Methods 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 11
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims description 3
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 27
- 239000003792 electrolyte Substances 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 238000007086 side reaction Methods 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 description 19
- 239000002002 slurry Substances 0.000 description 15
- 229910052681 coesite Inorganic materials 0.000 description 14
- 229910052906 cristobalite Inorganic materials 0.000 description 14
- 229910052682 stishovite Inorganic materials 0.000 description 14
- 229910052905 tridymite Inorganic materials 0.000 description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 12
- 239000010703 silicon Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 230000008859 change Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910001556 Li2Si2O5 Inorganic materials 0.000 description 7
- 239000004480 active ingredient Substances 0.000 description 7
- 238000009616 inductively coupled plasma Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 229910020489 SiO3 Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229910021419 crystalline silicon Inorganic materials 0.000 description 5
- 229910052909 inorganic silicate Inorganic materials 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 4
- 229910052912 lithium silicate Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- 229910007562 Li2SiO3 Inorganic materials 0.000 description 3
- 229910014604 LixSiOy Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H01M4/386—Silicon or alloys based on silicon
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Abstract
The invention provides a silica negative electrode material, a preparation method of the silica negative electrode material and a lithium ion battery, wherein the silica negative electrode material comprises an inner core, a modification layer and a coating layer which are sequentially distributed from inside to outside; wherein, the inner core is silicon dioxide and nano silicon distributed in the silicon dioxide; the modified layer is lithium disilicate, silicon dioxide and nano silicon distributed in the lithium disilicate and the silicon dioxide; the coating layer is carbon. The silicon-oxygen cathode material provided by the invention is beneficial to improving the conductivity of the material and reducing the contact between the material and an electrolyte, so that the occurrence of side reactions is reduced, and the cycle stability of the silicon-oxygen cathode material is improved.
Description
Technical Field
The invention relates to the technical field of battery cathode materials, in particular to a silica cathode material, a preparation method of the silica cathode material and a lithium ion battery.
Background
With the continuous update of electronic products and the rapid development of electric vehicles, the demand for high energy density lithium ion batteries is increasing day by day. The traditional lithium ion battery takes graphite as a negative electrode material, the current graphite negative electrode is difficult to meet the requirement of the lithium ion battery with high energy density on the market, and the negative electrode material of the lithium ion battery is promoted to develop towards a material direction with high theoretical capacity, wherein, because silicon has the advantages of high theoretical capacity, good safety performance, wide source and the like, the silicon becomes the mainstream of the research of novel negative electrode materials; however, the silicon negative electrode material has a defect of high side reaction with the electrolyte, so that the cycling stability is poor, and the application of the silicon negative electrode material in the lithium ion battery is limited.
Disclosure of Invention
The invention solves the problem that the silicon cathode material has poor cycle stability.
In order to solve the problems, the invention provides a silicon-oxygen anode material which comprises an inner core, a modified layer and a coating layer which are sequentially distributed from inside to outside; wherein,
the inner core is silicon dioxide and nano silicon distributed in the silicon dioxide;
the modified layer is lithium disilicate, silicon dioxide and nano silicon distributed in the lithium disilicate and the silicon dioxide;
the coating layer is carbon.
Optionally, the particle size ranges of the nano-silicon in the inner core and the modification layer are both 1 nm-10 nm.
Another object of the present invention is to provide a method for preparing the silicon-oxygen anode material, which comprises the following steps:
mixing a silicon monoxide with a lithium-containing compound to obtain a mixture;
carrying out heat treatment on the mixture in vacuum or inert atmosphere to obtain a pretreated mixture;
and carrying out carbon coating on the pretreated mixture to obtain the silicon-oxygen cathode material.
Another object of the present invention is to provide a method for preparing the silicon-oxygen anode material, which comprises the following steps:
carrying out carbon coating on the silicon monoxide to obtain carbon-coated silicon monoxide;
mixing the carbon-coated silicon monoxide with a lithium-containing compound to obtain a precursor;
and carrying out heat treatment on the precursor in vacuum or inert atmosphere to obtain the silicon-oxygen cathode material.
Optionally, the heat treatment comprises: and heating to 400-600 ℃, keeping the temperature for 2-6 hours, then continuing heating to 700-900 ℃, and keeping the temperature for 2-6 hours.
Optionally, the heating rate in the heat treatment process is 2 ℃/min-10 ℃/min.
Optionally, the carbon coating method is a chemical vapor deposition method.
Optionally, the lithium-containing compound is selected from at least one of lithium hydroxide, lithium carbonate, lithium acetate, and lithium oxalate.
Optionally, the mass percentage of the lithium element in the precursor ranges from 0.2% to 5%.
The invention further aims to provide a lithium ion battery, which comprises the silicon-oxygen negative electrode material.
Compared with the prior art, the silicon-oxygen anode material provided by the invention has the following advantages:
the silicon-oxygen cathode material provided by the invention is beneficial to improving the conductivity of the material and reducing the contact between the material and an electrolyte, so that the occurrence of side reactions is reduced, and the cycle stability of the silicon-oxygen cathode material is improved.
Drawings
FIG. 1 is a schematic structural diagram of a silicon-oxygen anode material according to the present invention;
FIG. 2 is an X-ray diffraction pattern of a silicon-oxygen anode material prepared in example 1 of the present invention;
FIG. 3 is an SEM topography of a silicon-oxygen cathode material prepared in example 1 of the present invention;
FIG. 4 is a macro topography of a pole piece prepared in example 1 of the present invention;
FIG. 5 is an X-ray diffraction pattern of a silicon-oxygen negative electrode material prepared in comparative example 1 of the present invention;
FIG. 6 is a macro topography of a pole piece prepared in comparative example 1 of the present invention;
FIG. 7 is an SEM topography of a silicon-oxygen cathode material prepared in comparative example 2 of the invention.
Description of reference numerals:
1-kernel; 2-a modified layer; and 3-coating layer.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the drawings are exemplary and intended to be illustrative of the present invention and should not be construed as limiting the present invention, and all other embodiments that can be obtained by one skilled in the art based on the embodiments of the present invention without inventive efforts shall fall within the scope of protection of the present invention.
In the description of the present invention, it is to be understood that the terms "first" and "second" are used merely for simplifying the description, and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
In order to solve the problem of poor cycle stability of the silicon negative electrode material, the invention provides a silicon-oxygen negative electrode material, which is shown in figure 1 and comprises an inner core 1, a modified layer 2 and a coating layer 3 which are sequentially distributed from inside to outside; wherein, the inner core 1 is made of silicon dioxide and nano silicon distributed in the silicon dioxide; the modified layer 2 is coated on the outer side of the inner core 1, and the modified layer 2 is lithium disilicate (Li)2Si2O5) And silicon dioxide, and distribution in lithium disilicate and in silicon dioxideNano silicon in silicon; the coating layer 3 is coated on the outer side of the modified layer 2, and the coating layer 3 is carbon.
According to the silicon-oxygen negative electrode material, the composite structure with the modification layer and the coating layer is designed, so that on one hand, the loss of lithium intercalation for the first time is reduced through the coating layer, and the first efficiency is improved; on the other hand by Li in the intermediate modified layer 22Si2O5Using Li2Si2O5The characteristics of low Li content and difficult dissolution improve the water resistance of the surface of the silicon-oxygen negative electrode material, thereby improving the stability of the slurry.
In addition, a certain amount of nano silicon exists in the modified layer 2, which is beneficial to improving the content of active components in the silicon-oxygen anode material, so that the specific capacity of the silicon-oxygen anode material is improved.
The silicon-oxygen cathode material provided by the invention is beneficial to improving the conductivity of the material and reducing the contact between the material and an electrolyte, so that the occurrence of side reactions is reduced, and the cycle stability of the silicon-oxygen cathode material is improved.
Furthermore, the particle size ranges of the nano silicon in the inner core 1 and the modified layer 2 are preferably 1 nm-10 nm.
Further, the concentration (at%) of Li element in the modified layer 2 decreases from the outside to the inside, and the Si/O ratio increases from the outside to the inside.
Another object of the present invention is to provide a method for preparing a silicon-oxygen negative electrode material as described above, the method comprising a process of modifying a lithium-containing compound by heat treatment and a carbon coating process, wherein the carbon coating process can be performed after or before the modification of the lithium-containing compound; specifically, the preparation method for carbon coating after modification of the lithium-containing compound comprises the following steps:
mixing a silicon monoxide with a lithium-containing compound to obtain a mixture;
carrying out heat treatment on the mixture in vacuum or inert atmosphere to obtain a pretreated mixture;
and carrying out carbon coating on the pretreated mixture to obtain the silicon-oxygen cathode material.
Or, the preparation method for carbon coating before the modification of the lithium-containing compound comprises the following steps:
carrying out carbon coating on the silicon monoxide to obtain carbon-coated silicon monoxide;
mixing carbon-coated silicon monoxide with a lithium-containing compound to obtain a precursor;
and carrying out heat treatment on the precursor in vacuum or inert atmosphere to obtain the silicon-oxygen cathode material.
In the application, the mass ratio of the mass of the lithium element in the lithium-containing compound to the mass of the silicon monoxide is preferably (1-10): 100, respectively; the total mass ratio of carbon in the silicon-oxygen negative electrode material is 1-10 wt%.
Wherein, during the heat treatment, the silicon monoxide forms the inner core 1; further, the lithium-containing compound reacts with silicon dioxide on the surface of the inner core 1 to form a modified layer 2 coated on the outer side of the inner core 1, wherein the modified layer 2 is lithium disilicate generated after the lithium-containing compound reacts with the silicon dioxide and nanometer silicon which does not participate in the reaction; and then combining a carbon coating layer generated in the carbon coating process, namely a coating layer 3 coated on the outer side of the modified layer 2, so as to obtain the silicon-oxygen negative electrode material provided by the application.
The preparation method of the silicon-oxygen cathode material provided by the invention is simple in preparation process, wide in application prospect and easy for large-scale generation; aiming at the problems that in the prior art, a silica negative electrode material has more side reactions with electrolyte and low first efficiency, lithium silicate is modified to react off silicon dioxide on the surface of the material to form a modified layer 2, so that the loss of first lithium intercalation is reduced, and the first efficiency is improved; meanwhile, the modified layer 2 is insoluble in water and has good water resistance, so that the stability of the slurry is improved.
Further, when the lithium salt is modified by heat treatment, the heat treatment process is preferably a two-stage heat treatment process, and preferably the heat treatment comprises: heating to 400-600 ℃, keeping the temperature for 2 hours, then continuing heating to 700-900 ℃, and keeping the temperature for 2 hours.
When the temperature is raised to a low temperature range of 400-600 ℃, the lithium-containing compound reacts with the silicon dioxide phase in the silica material to generate water-soluble Li with high lithium content2SiO3Or Li4SiO4With a lithium-containing compound asFor example, lithium carbonate has the following specific reaction formula:
Li2CO3+SiO2→LixSiOy+CO2↑；
also, in this temperature regime, the lower temperature also inhibits the lithium-containing compound from reacting with the silicon phase in the silicon oxygen material, for example, inhibits the lithium carbonate from reacting with the silicon phase as follows:
Li2CO3+Si→LixSiOy+C，
or, Li2CO3+Si→LixSiOy+CO↑；
Thereby helping to reduce the loss of active ingredient.
When the temperature is raised to a high-temperature section of 700-900 ℃, the lithium ions are promoted to be thermally diffused into the silica material, the phase change between silicates is realized, and the water-soluble Li with high Li content2SiO3Or Li4SiO4Conversion to low Li content and insoluble Li2Si2O5The reaction process is as follows:
Li4SiO4+SiO2→2Li2SiO3；
Li2SiO3+SiO2→Li2Si2O5。
in the pre-lithiated silica materials prepared in the prior art, the lithium silicate phase composition typically includes Li4SiO4、Li2SiO3And Li2Si2O5One or more of them, poor controllability; the application obtains uniform and single-component Li in the modified layer 2 by adopting a two-stage heat treatment process2Si2O5Using lithium disilicate (Li)2Si2O5) The lithium-ion battery has low lithium content and indissolvability, is beneficial to improving the water resistance of the surface of the silica negative electrode material, can prevent soluble lithium silicate from being separated out on the surface of an electrode after a pole piece is dried when being used for a lithium ion battery, and avoids Li with strong water solubility2SiO3Or Li4SiO4The water system slurry is in strong alkalinity, and the effect of the adhesive is influenced.
Further, the temperature rise rate in the heat treatment process is preferably in the range of 2 ℃/min to 10 ℃/min, and further preferably 5 ℃/min.
The preferred method of carbon coating in this application is chemical vapor deposition.
In order to ensure that the reaction is smoothly carried out, a lithium-containing compound is preferably used as a material which is easy to decompose thermally, and specifically, a lithium salt is preferably selected from at least one of lithium hydroxide, lithium carbonate, lithium acetate and lithium oxalate; and the mass percentage range of lithium element in the raw material is preferably 0.2-5%, so that the cycling stability and the specific capacity of the silicon-oxygen negative electrode material are considered at the same time.
According to the preparation method of the silica negative electrode material, the prepared silica negative electrode material with the modification layer and the coating layer can improve the conductivity of the silica negative electrode material and reduce the contact between the material and electrolyte, so that the occurrence of side reactions is reduced, and the cycle stability of the silica negative electrode material is improved; meanwhile, the modified layer 2 is formed by converting the inactive part in the material, so that the first efficiency of the silicon-oxygen anode material can be further improved.
XRD detection is carried out on the silicon-oxygen anode material prepared by the invention, and the peak intensity ratio of each substance measured according to XRD meets the condition that the Li is more than 0.5 and less than I2Si2O5(111)]/I[Si(111)]＜2.5，0.5＜I[SiO2(101)]/I[Si(111)]＜1.6。
It is still another object of the present invention to provide a lithium ion battery, which includes the above-mentioned silicon-oxygen negative electrode material.
The lithium ion battery provided by the invention is beneficial to improving the first efficiency and the cycle performance of the lithium ion battery by adopting the silica negative electrode material.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
Example 1
The embodiment provides a preparation method of a silicon-oxygen anode material.
S1: weighing 475g of silicon monoxide, placing the silicon monoxide in a rotary furnace, and heating to 900 ℃ under the protection of nitrogen atmosphere; after the temperature is stable, introducing ethylene gas into the rotary furnace at the speed of 0.5L/min, continuing for 2 hours, and cooling to obtain 500g of carbon-coated silicon monoxide;
s2: uniformly mixing carbon-coated silicon monoxide and 25g of lithium acetate by using a V-shaped mixer under the protection of argon gas to obtain a precursor (the content of lithium element is 0.5 wt%);
s3: and putting the precursor into a vacuum reaction furnace, reducing the pressure to 10Pa, heating from room temperature to the first heat treatment temperature of 400 ℃ at the speed of 5 ℃/min, preserving the heat for 6h, then heating to the second heat treatment temperature of 800 ℃ at the speed of 5 ℃/min, preserving the heat for 4h, naturally cooling, and collecting the product to obtain the silicon-oxygen cathode material.
When the silicon oxide negative electrode material obtained in this example was subjected to X-ray diffraction (XRD) analysis, as shown in fig. 2, a peak (111) ascribed to Si crystal was present in the vicinity of a diffraction angle (2 θ) of 28.5 °, and a peak having a large intensity ascribed to Li in the range of 23.8 to 24.9 ° was present in the diffraction angle (2 θ)2Si2O5The (130), (040), (111) peaks of the crystals, which are classified as SiO as having smaller intensity near the diffraction angle (2 theta) of 26.6 DEG2Peak (101) of crystal. I [ Li ]2Si2O5(111)]/I[Si(111)] = 2.22，I[SiO2(101)]/I[Si(111)] = 0.97。
Analysis was performed using the scherrer equation (sherrer equation) based on the Si (111) peak attributed to around 28.5 ° in the XRD pattern:
Crystal size (nm) = K·λ/(B·cosθ)
where K =0.9, λ ═ 0.154nm, B = full width at half maximum (FWHM, rad), and θ = peak position (angle), it was found that the Si crystal size (crystal size) in the obtained silicon oxygen anode material was 5.6 nm; in addition, amorphous silicon dioxide and carbon are also present in the silicon-oxygen cathode material, and the silicon-oxygen cathode material is analyzed by a Scanning Electron Microscope (SEM), and the result is shown in figure 3, and the carbon-coated silicon-oxygen material is modified by lithium acetate heat treatment, so that the surface carbon layer is kept intact.
Silicon-oxygen cathode material prepared in this example using inductively coupled plasma spectroscopy (ICP)Analysis shows that the content of lithium element in the silicon-oxygen negative electrode material prepared in the embodiment is 0.47 wt%; calculated, corresponding Li2Si2O5The content of (B) was 5.06 wt%.
Taking the silica negative electrode material prepared in the embodiment as a negative electrode active component, mixing the silica negative electrode material with a conductive agent (Super-P) and a binder (LA 136D) according to a mass ratio of 80:10:10, adding a dispersant (water) to prepare slurry, coating the slurry on a copper foil, performing vacuum drying and rolling, and observing whether salt is separated from the surface of a pole piece, wherein the result is shown in FIG. 4; therefore, the silicon-oxygen negative electrode material prepared by the method is uniform and stable, and has no precipitate.
The pole piece is used as a negative electrode, the metal lithium is used as a positive electrode, the cycle performance of the pole piece in the lithium ion battery is tested, the charge-discharge cycle test is carried out at the current of 150mA/g, the charge-discharge voltage interval is 1.5-0.005V, and the specific test data are shown in Table 1.
Transferring 5mL of the slurry to a vacuum aluminum-plastic sealing bag, standing for 48 hours, observing the expansion condition of the sealing bag, and measuring the volume change by adopting a drainage method, wherein the gas production rate is = (the volume change of the aluminum-plastic sealing bag before and after standing)/5 mL multiplied by 100%; the result shows that the surface of the pole piece prepared by taking the silicon-oxygen negative electrode material as a negative active ingredient is free from salt analysis after drying, and the color is uniform; the slurry is kept stand for 48 hours without volume change, and the gas production rate is 0 percent.
Example 2
In this example, the amount of lithium acetate added was 10g (lithium element content in precursor: 0.2 wt%), and the rest was the same as in example 1.
The silicon-oxygen anode material prepared in this example was tested, and the specific testing process is described in example 1.
XRD result shows that the silicon-oxygen cathode material prepared in the embodiment contains crystalline Si and Li inside2Si2O5And SiO2，I[Li2Si2O5(111)]/I[Si(111)] = 1.65，I[SiO2(101)]/I[Si(111)]= 1.26, Si crystal size (crystal size) 5.5 nm; in addition, amorphous SiO also exists in the silicon-oxygen cathode material2And carbon.
SEM results show that 5wt% carbon-coated silica material has the surface carbon layer intact after modification by lithium acetate (Li used 0.2 wt%) heat treatment.
The ICP results showed that the silicon-oxygen negative electrode material (Li) prepared in this example had a content of 0.18wt%, and the corresponding Li was calculated2Si2O5The mass fraction of (A) was 1.94 wt%.
After being dried, the pole piece prepared by taking the silica negative material as a negative active ingredient has no salt on the surface and uniform color; the slurry was left to stand for 48 hours and the volume increased by 0.5mL, with a gas production rate of 10%.
The cycle performance test data is detailed in table 1.
Example 3
The lithium salt in step S2 of this example was lithium carbonate, the lithium carbonate was added in an amount of 14g, and the temperature of the first heat treatment in step S3 was 600 ℃ and the rest was the same as in example 1.
The silicon-oxygen anode material prepared in this example was tested, and the specific testing process is described in example 1.
XRD result shows that the silicon-oxygen anode material prepared in the embodiment contains crystalline Si and Li inside2Si2O5And SiO2Crystal of I [ Li ]2Si2O5(111)]/I[Si(111)] = 1.92，I[SiO2(101)]/I[Si(111)]= 1.31, Si crystal size (crystal size) 5.7 nm; in addition, amorphous SiO also exists in the silicon-oxygen cathode material2And carbon.
SEM results show that the surface carbon layer remained intact after 5wt% carbon coated silica material was modified by heat treatment with lithium carbonate (Li used 0.5 wt%).
The ICP results show that the silicon-oxygen anode material prepared in the example has a lithium (Li) content of 0.48wt%, and the corresponding Li is calculated2Si2O5The content was 5.1%.
After being dried, the pole piece prepared by taking the silica negative material as a negative active ingredient has no salt on the surface and uniform color; the slurry is kept stand for 48 hours without volume change, and the gas production rate is 0 percent.
The cycle performance test data is detailed in table 1.
Example 4
The second heat treatment temperature in step S3 of this example was 900 ℃, and the rest was the same as in example 1.
The silicon-oxygen anode material prepared in this example was tested, and the specific testing process is described in example 1.
XRD result shows that the silicon-oxygen anode material prepared in the embodiment contains crystalline Si and Li inside2Si2O5And SiO2Crystal of I [ Li ]2Si2O5(111)]/I[Si(111)] = 1.21，I[SiO2(101)]/I[Si(111)]= 1.15, Si crystal size (crystal size) 6.2 nm; in addition, amorphous SiO also exists in the silicon-oxygen cathode material2And carbon.
SEM results show that 5wt% carbon-coated silica material was modified by a lithium acetate (Li used 0.5 wt%) heat treatment to leave the surface carbon layer intact.
The ICP results show that the silicon-oxygen anode material prepared in the example has a lithium (Li) content of 0.48wt%, and the corresponding Li is calculated2Si2O5The content was 5.19%.
After being dried, the pole piece prepared by taking the silica negative material as a negative active ingredient has no salt on the surface and uniform color; the slurry is kept stand for 48 hours without volume change, and the gas production rate is 0 percent.
The cycle performance test data is detailed in table 1.
Comparative example 1
S1: weighing 475g of silicon monoxide, placing the silicon monoxide in a rotary furnace, and heating to 900 ℃ under the protection of nitrogen atmosphere; after the temperature is stable, introducing ethylene gas into the rotary furnace at the speed of 0.05L/min, continuing for 2 hours, and cooling to obtain 500g of carbon-coated silicon monoxide;
s2: uniformly mixing carbon-coated silicon monoxide and 416g of lithium acetate by using a V-shaped mixer under the protection of argon gas to obtain a precursor;
s3: and putting the precursor into a vacuum reaction furnace, reducing the pressure to 10Pa, heating to 600 ℃ from room temperature at the speed of 5 ℃/min, preserving the temperature for 2h, naturally cooling, and collecting a product to obtain the silica negative electrode material.
The silicon-oxygen anode material prepared by the comparative example is tested, and the specific testing process is described in example 1.
XRD results are shown in FIG. 5, and the silicon-oxygen anode material prepared by the comparative example internally contains crystalline Si and Li2SiO3And SiO2Crystal of I [ SiO ]2(101)]/I[Si(111)]= 0.62, Si crystal size (crystal size) 5.7 nm; in addition, amorphous SiO also exists in the silicon-oxygen cathode material2And carbon.
SEM results show that the surface carbon layer remained intact after 5wt% carbon-coated silica material was modified by lithium acetate (Li used 5.0 wt%) heat treatment.
The ICP results showed that the lithium (Li) content of the silicon-oxygen negative electrode material prepared in this comparative example was 4.52wt%, and the corresponding Li was calculated2SiO3The content was 29.3%.
The surface morphology of the pole piece prepared by taking the silica negative electrode material as a negative electrode active ingredient is shown in figure 6 after drying, and a large amount of white salt is separated out; the volume change of the slurry is more than 5mL after the slurry is kept stand for 48 hours, and the gas production rate is more than 100 percent; the pH value of the slurry is 12.36, and the slurry is strongly alkaline.
The cycle performance test data is detailed in table 1.
Comparative example 2
S1: uniformly mixing 500g of silicon monoxide and 25g of lithium acetate by using a V-shaped mixer under the protection of argon gas to obtain a precursor;
s2: and putting the precursor into a vacuum reaction furnace, reducing the pressure to 10Pa, heating from room temperature to the first heat treatment temperature of 400 ℃ at the speed of 5 ℃/min, preserving the heat for 6h, then heating to the second heat treatment temperature of 800 ℃ at the speed of 5 ℃/min, preserving the heat for 4h, naturally cooling, and collecting the product to obtain the silicon-oxygen cathode material.
The silicon-oxygen anode material prepared by the comparative example is tested, and the specific testing process is described in example 1.
XRD result shows that the silicon-oxygen cathode material prepared by the comparative example contains crystalline Si and Li inside2Si2O5And SiO2，I[Li2Si2O5(111)]/I[Si(111)] = 1.01，I[SiO2(101)]/I[Si(111)]= 0.62, Si crystal size (crystal size) 6.5 nm; in addition, amorphous SiO also exists in the silicon-oxygen cathode material2And carbon.
Referring to fig. 7, SEM results show that after the silicon oxide material is modified by lithium acetate (Li is used in an amount of 0.5 wt%), the surface is roughened, and a uniform lithium silicate coating modified layer is formed by XRD analysis.
The ICP results showed that the silicon-oxygen negative electrode material prepared in this comparative example had a lithium (Li) content of 0.49wt%, and the corresponding Li was calculated2Si2O5The content is 5.30%.
After being dried, the pole piece prepared by taking the silica negative material as a negative active ingredient has no salt on the surface and uniform color; the slurry is kept stand for 48 hours without volume change, and the gas production rate is 0 percent.
The cycle performance and rate performance test data are detailed in table 1.
TABLE 1
From the above data, it can be seen that the material of the present invention consumes SiO with low electrochemical reactivity during the preparation process2The first coulombic efficiency of the composite material is obviously improved, and meanwhile, the contact between the electrolyte and the material is cut off due to the existence of the coating layer, so that the circulation stability of the composite material is greatly improved.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present disclosure, and such changes and modifications will fall within the scope of the present invention.
Claims (10)
1. The silicon-oxygen cathode material is characterized by comprising an inner core (1), a modified layer (2) and a coating layer (3) which are sequentially distributed from inside to outside; wherein,
the inner core (1) is silicon dioxide and nano silicon distributed in the silicon dioxide;
the modified layer (2) is lithium disilicate and silicon dioxide, and nano silicon distributed in the lithium disilicate and the silicon dioxide;
the coating layer (3) is carbon.
2. The silicon-oxygen anode material as claimed in claim 1, wherein the particle size of the nano-silicon in the inner core (1) and the particle size of the nano-silicon in the modification layer (2) are both in the range of 1nm to 10 nm.
3. A method for preparing a silicon-oxygen anode material according to claim 1 or 2, characterized by comprising the following steps:
mixing a silicon monoxide with a lithium-containing compound to obtain a mixture;
carrying out heat treatment on the mixture in vacuum or inert atmosphere to obtain a pretreated mixture;
and carrying out carbon coating on the pretreated mixture to obtain the silicon-oxygen cathode material.
4. A method for preparing a silicon-oxygen anode material according to claim 1 or 2, characterized by comprising the following steps:
carrying out carbon coating on the silicon monoxide to obtain carbon-coated silicon monoxide;
mixing the carbon-coated silicon monoxide with a lithium-containing compound to obtain a precursor;
and carrying out heat treatment on the precursor in vacuum or inert atmosphere to obtain the silicon-oxygen cathode material.
5. The method of preparing a silicon oxygen anode material of claim 4, wherein the heat treatment comprises: and heating to 400-600 ℃, keeping the temperature for 2-6 hours, then continuing heating to 700-900 ℃, and keeping the temperature for 2-6 hours.
6. The preparation method of the silicon-oxygen anode material as claimed in claim 5, wherein the heating rate in the heat treatment process is 2 ℃/min to 10 ℃/min.
7. The method for preparing a silicon-oxygen anode material according to claim 4, wherein the carbon coating method is a chemical vapor deposition method.
8. The method for preparing a silicon-oxygen negative electrode material according to any one of claims 4 to 7, wherein the lithium-containing compound is at least one selected from lithium hydroxide, lithium carbonate, lithium acetate and lithium oxalate.
9. The method for preparing a silicon-oxygen anode material according to claim 8, wherein the mass percentage of lithium in the precursor is in the range of 0.2% to 5%.
10. A lithium ion battery comprising the silicon oxygen negative electrode material of claim 1 or 2.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114597374A (en) * | 2022-03-21 | 2022-06-07 | 上海兰钧新能源科技有限公司 | Silica anode material and preparation method thereof |
| CN114975967A (en) * | 2022-06-29 | 2022-08-30 | 宁波杉杉新材料科技有限公司 | Pre-lithiated silica composite material, preparation method thereof, negative pole piece, battery and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110024188A (en) * | 2016-11-30 | 2019-07-16 | 松下知识产权经营株式会社 | Negative electrode material and non-aqueous electrolyte secondary battery |
| JP2020004482A (en) * | 2018-06-25 | 2020-01-09 | 信越化学工業株式会社 | Method for producing negative electrode active material for nonaqueous electrolyte secondary battery, negative electrode active material for nonaqueous electrolyte secondary battery, negative electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery |
| CN111900368A (en) * | 2020-07-24 | 2020-11-06 | 陕西煤业化工技术研究院有限责任公司 | Lithium ion battery-grade silicon monoxide negative electrode material, and preparation method and application thereof |
| CN112186188A (en) * | 2020-09-29 | 2021-01-05 | 东莞东阳光科研发有限公司 | Silicon-based negative electrode material and preparation method and application thereof |
| CN112803015A (en) * | 2019-11-14 | 2021-05-14 | 贝特瑞新材料集团股份有限公司 | Negative electrode material, preparation method thereof and lithium ion battery |
-
2021
- 2021-12-30 CN CN202111635820.4A patent/CN114005974B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110024188A (en) * | 2016-11-30 | 2019-07-16 | 松下知识产权经营株式会社 | Negative electrode material and non-aqueous electrolyte secondary battery |
| JP2020004482A (en) * | 2018-06-25 | 2020-01-09 | 信越化学工業株式会社 | Method for producing negative electrode active material for nonaqueous electrolyte secondary battery, negative electrode active material for nonaqueous electrolyte secondary battery, negative electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery |
| CN112803015A (en) * | 2019-11-14 | 2021-05-14 | 贝特瑞新材料集团股份有限公司 | Negative electrode material, preparation method thereof and lithium ion battery |
| CN111900368A (en) * | 2020-07-24 | 2020-11-06 | 陕西煤业化工技术研究院有限责任公司 | Lithium ion battery-grade silicon monoxide negative electrode material, and preparation method and application thereof |
| CN112186188A (en) * | 2020-09-29 | 2021-01-05 | 东莞东阳光科研发有限公司 | Silicon-based negative electrode material and preparation method and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114597374A (en) * | 2022-03-21 | 2022-06-07 | 上海兰钧新能源科技有限公司 | Silica anode material and preparation method thereof |
| CN114597374B (en) * | 2022-03-21 | 2024-02-09 | 上海兰钧新能源科技有限公司 | Silicon-oxygen negative electrode material and preparation method thereof |
| CN114975967A (en) * | 2022-06-29 | 2022-08-30 | 宁波杉杉新材料科技有限公司 | Pre-lithiated silica composite material, preparation method thereof, negative pole piece, battery and application |
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