CN114373891A - Composite lithium negative electrode and application thereof - Google Patents
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 107
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 239000010954 inorganic particle Substances 0.000 claims abstract description 52
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 16
- 125000000524 functional group Chemical group 0.000 claims abstract description 10
- 125000003172 aldehyde group Chemical group 0.000 claims abstract description 8
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 229910012377 LiSix Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 7
- -1 sulfydryl Chemical group 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 15
- 229910001416 lithium ion Inorganic materials 0.000 description 15
- 210000001787 dendrite Anatomy 0.000 description 13
- 235000012239 silicon dioxide Nutrition 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
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- 239000003792 electrolyte Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910052743 krypton Inorganic materials 0.000 description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052704 radon Inorganic materials 0.000 description 2
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
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- 239000011248 coating agent Substances 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000013385 inorganic framework Substances 0.000 description 1
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 description 1
- IDNHOWMYUQKKTI-UHFFFAOYSA-M lithium nitrite Chemical compound [Li+].[O-]N=O IDNHOWMYUQKKTI-UHFFFAOYSA-M 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 239000012982 microporous membrane Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- 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
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Abstract
The invention provides a composite lithium negative electrode and application thereof, wherein the composite lithium negative electrode comprises lithium metal and functionalized inorganic particles; the functional group of the functionalized inorganic particle comprises any one or the combination of at least two of carboxyl, carbonyl, hydroxyl, sulfydryl, aldehyde group, peptide bond, carbon-carbon double bond, carbon-carbon triple bond or nitro; the invention solves the problems of volume expansion and lithium dendritic crystal growth of lithium metal in the circulation process by adding functionalized inorganic particles in the lithium metal.
Description
Technical Field
The invention belongs to the technical field of batteries, relates to a lithium cathode, and particularly relates to a composite lithium cathode and application thereof.
Background
Lithium metal negative electrodes have a high theoretical specific capacity (3860mAh/g) which is ten times that of the graphite negative electrodes commercialized at present (372mAh/g), and therefore, the adoption of lithium metal as the negative electrode of a power battery has been widely concerned.
The high reactivity of the lithium metal negative electrode results in a large consumption of lithium, which makes it easy for lithium dendrite growth to occur during the lithium ion deintercalation process, thereby puncturing the separator, and volume expansion and the like may occur during the lithium negative electrode cycling process. While lithium anodes have great potential development space, the mere use of pure lithium metal as the anode does not allow long cycling of the battery.
Based on the research, how to provide a composite lithium negative electrode can solve the problems that lithium metal has overlarge volume expansion in charge-discharge cycles, lithium dendrite grows to pierce a diaphragm and the like.
Disclosure of Invention
The invention aims to provide a composite lithium negative electrode and application thereof, in particular to a composite lithium negative electrode supported by an inorganic framework and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a composite lithium anode comprising lithium metal, and functionalized inorganic particles;
the functional group of the functionalized inorganic particle includes any one or a combination of at least two of a carboxyl group, a carbonyl group, a hydroxyl group, a mercapto group, an aldehyde group, a peptide bond, a carbon-carbon double bond, a carbon-carbon triple bond, or a nitro group, and typical, but non-limiting, combinations include a combination of a carboxyl group and a carbonyl group, a combination of a hydroxyl group and a mercapto group, a combination of an aldehyde group and a carbon-carbon double bond, or a combination of a carbon-carbon triple bond and a nitro group.
The functionalized inorganic particles play a role of an inorganic skeleton in the composite lithium cathode, and when pure lithium metal is adopted as the cathode, the lithium metal reacts with electrolyte in a circulation process, a passivation layer is formed on the surface of the lithium metal, the ionic conductivity is poor, the strength is low, the electrolyte is continuously consumed, and meanwhile, the interface resistance of the lithium metal and the electrolyte is higher and higher; therefore, this application adopts the inorganic granule of functional group to support lithium metal, can accelerate the conduction of lithium ion, promotes the ionic conduction rate of compound lithium negative pole, reduces the inhomogeneous deposit of lithium ion, promotes the ability of anti negative pole inflation to can restrain the growth of lithium dendrite.
The mechanism of bonding the functionalized inorganic particles to lithium metal according to the present invention includes: carboxyl, carbonyl, hydroxyl, sulfydryl, aldehyde group and peptide bond can generate substitution reaction with lithium metal, so that the inorganic particles are bonded with the lithium metal; the carbon-carbon double bond and the carbon-carbon triple bond can generate addition reaction bonding with lithium metal; lithium metal and nitro groups generate inorganic substances such as lithium nitrite and lithium nitride.
In the functionalized inorganic particles of the present invention, the number of functional groups is 1 or more, and may be, for example, 3, 5, 10, 15, 20, 25, 30 or 35, but is not limited to the recited values, and other positive integers not recited within the numerical range are also applicable.
The functionalized inorganic particles may have a molar ratio of any two functional groups of 1 (0.1 to 10), such as 1:0.1, 1:1, 1:5, or 1:10, but are not limited to the recited values, and other values not recited within the range are equally applicable.
The functionalized inorganic particles may have a molar ratio of any three functional groups of 1 (0.1 to 10) to (0.1 to 10), and may be, for example, 1:0.1:0.1, 1:1:1, 1:5:10, or 1:10:10, but are not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the functionalized inorganic particles have a young's modulus of 1GPa or more, for example, 1GPa, 1.5GPa, 2GPa, 2.5GPa, 3GPa, 3.5GPa, 4GPa, 4.5GPa, 5GPa, 6GPa or 8GPa, but not limited to the values listed, and other values not listed in the numerical range are also applicable, preferably 1GPa to 6 GPa.
The functionalized inorganic particles have a Young's modulus of more than 1GPa, so that the growth of lithium dendrites can be inhibited, lithium metal is stabilized, the expansion effect of the lithium negative electrode in an inorganic particle network is reduced, and the volume expansion of the lithium negative electrode is inhibited, and when the Young's modulus of the functionalized inorganic particles is less than 1GPa, the effects of inhibiting the generation of the lithium dendrites and the expansion of the lithium metal are difficult to achieve.
Preferably, the functionalized inorganic particles have an ionic conductivity of 10-5S/cm to 10-3S/cm, e.g. may be 10-5S/cm、10-4S/cm or 10-3S/cm, but is not limited to the values recited, other values within the range of values not recited are equally applicable.
The functionalized inorganic particles have high ionic conductivity, so that the phenomenon of lithium dendritic crystal growth caused by uneven deposition of lithium ions in the charge-discharge cycle process can be avoided.
Preferably, the functionalized inorganic particles have a particle size D50From 100nm to 600nm, for example 100nm, 200nm, 300nm, 400nm, 500nm or 600nm, but are not limited to the values listed, and other values not listed in the numerical range are likewise suitable.
Preferably, the inorganic particles comprise silicon-based inorganic particles.
Preferably, the silicon-based inorganic particles include silica and/or LiSixOyWherein x > 0 and y > 0.
The silicon-based inorganic particles comprise LiSixOyWhere x > 0, for example, is 0.1, 0.3, 0.5, 0.7, 0.9, 1.1 or 1.3, but is not limited to the values listed, other values not listed in the numerical range are equally suitable, preferably 0 < x < 1.
The silicon-based inorganic particles comprise LiSixOyWhere y > 0, for example, is 0.1, 0.3, 0.5, 0.7, 0.9, 1.1 or 1.3, but is not limited to the values listed, and other values not listed in the numerical range are equally suitable, preferably 0 < x < 3.
The preparation method of the composite lithium negative electrode comprises the following steps:
and mixing lithium metal and the functionalized inorganic particles under the inert gas condition to obtain the composite lithium negative electrode.
Preferably, the lithium metal is in a molten state.
Preferably, the inert gas comprises helium, argon, krypton or radon, with typical but non-limiting combinations comprising a combination of helium and argon, or krypton and radon.
Preferably, the mixing is stirred mixing.
Preferably, after the mixing is finished, the temperature is reduced to obtain the lithium composite negative electrode.
In a second aspect, the present invention provides an electrochemical device comprising a composite lithium negative electrode as described in the first aspect.
Preferably, the electrochemical device comprises a lithium ion battery.
In a third aspect, the present invention provides an electronic device comprising an electrochemical apparatus according to the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts the functionalized inorganic particles as the framework of the lithium cathode to improve the ion conduction rate of the composite lithium cathode, accelerate the conduction of lithium ions, reduce the uneven deposition of the lithium ions, improve the anti-expansion capability of the cathode and inhibit the growth of lithium dendrites, thereby obtaining the lithium ion battery with excellent cycle performance.
Drawings
Fig. 1 is a schematic view showing the surface state of a lithium composite negative electrode described in example 1 after 100 cycles.
Fig. 2 is a schematic view showing the surface state of the negative electrode described in comparative example 2 after 100 cycles.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The method for functionalizing inorganic particles comprises the following steps: the functionalized inorganic particles are obtained by combining inorganic particles with polymers through adsorption force, hydrogen bonds or covalent bonds and the like, and performing surface modification on the inorganic particles with different functional groups (comprising any one or the combination of at least two of carboxyl, carbonyl, hydroxyl, sulfydryl, aldehyde groups, peptide bonds, carbon-carbon double bonds, carbon-carbon triple bonds or nitro neutrality) by adopting silane coupling agents with different functional groups in an acidic or alkaline environment; the modification method is not particularly limited, and only the inorganic particles can realize functional group modification; the above description of the method for functionalizing inorganic particles is intended to more fully illustrate the technical solution of the present invention and should not be construed as a specific limitation to the present invention.
Example 1
The present embodiment provides a composite lithium anode comprising lithium metal and functionalized silica;
the functionalized silicon dioxide is silicon dioxide functionalized by carboxyl, carbonyl and hydroxyl, and the molar ratio of the carboxyl to the carbonyl to the hydroxyl is 1:1: 1;
the Young's modulus of the functionalized silicon dioxide is 2.9GPa, and the ionic conductivity is 2.4 multiplied by 10-4S/cm, particle diameter D50Is 300 nm;
the preparation method of the composite lithium negative electrode comprises the following steps:
and stirring and mixing molten lithium metal and functionalized silicon dioxide in an argon atmosphere, and cooling to obtain the composite lithium negative electrode.
Fig. 1 shows a schematic view of the surface state of the lithium composite negative electrode after 100 cycles.
Example 2
The present embodiment provides a composite lithium anode comprising lithium metal and functionalized silica;
the functionalized silicon dioxide is functionalized by adopting carbon-carbon double bonds and nitro groups, and the molar ratio of the carbon-carbon double bonds to the nitro groups is 1: 3;
the Young's modulus of the functionalized silicon dioxide is 2GPa, and the ionic conductivity is 1.1 x 10-4S/cm, particle diameter D50Is 100 nm;
the preparation method of the composite lithium negative electrode comprises the following steps:
and stirring and mixing molten lithium metal and functionalized silicon dioxide in an argon atmosphere, and cooling to obtain the composite lithium negative electrode.
Example 3
The present embodiment provides a composite lithium anode comprising lithium metal and functionalized silica;
the functionalized silicon dioxide is functionalized by adopting carbon-carbon triple bonds and aldehyde groups, and the molar ratio of the carbon-carbon triple bonds to the aldehyde groups is 1: 10;
the Young's modulus of the functionalized silicon dioxide is 1.2GPa, and the ionic conductivity is 1.3 multiplied by 10-4S/cm, particle diameter D50Is 600 nm;
the preparation method of the composite lithium negative electrode comprises the following steps:
and stirring and mixing molten lithium metal and functionalized silicon dioxide in a helium atmosphere, and cooling to obtain the composite lithium cathode.
Examples 4 and 5 the same as example 1 except that the kind of the functionalized inorganic particles was changed as shown in table 2.
Examples 6 and 7 were the same as example 1 except that the functionalized inorganic particles having the Young's modulus shown in Table 3 were used.
Examples 8 and 9 the same as example 1 except that the ion conductivity of the functionalized inorganic particles was changed as shown in table 4.
Comparative example 1 the procedure of example 1 was followed, except that as shown in Table 5, silica which had not been functionalized was used.
Comparative example 2 used a simple lithium metal as a negative electrode, and a schematic view of the surface state after 100 cycles was shown in fig. 2.
And (3) performance testing:
the composite lithium negative electrode provided by the embodiment and the negative electrode provided by the comparative example, the positive electrode, the diaphragm and the electrolyte are assembled into the lithium ion battery according to a general process for preparing the lithium ion battery; the positive electrode is obtained by coating and drying positive electrode slurry on an aluminum foil, wherein the positive electrode slurry comprises LNCM (LiNi) with the mass ratio of 95:3:2:500.8Co0.1Mn0.1O2) Acetylene black, polyvinylidene fluorideAlkenes and N-methylpyrrolidone; the diaphragm adopts a polypropylene microporous membrane (Celgard-2400); the electrolyte adopts 1mol/L LiPF6EC + DMC + EMC (EC is ethylene carbonate, EMC is ethyl methyl carbonate, DMC is dimethyl carbonate, and the volume ratio of EC, DMC and EMC is 1:1: 1).
And (3) carrying out a cycle performance test on the assembled lithium ion battery, and carrying out a test on the ionic conductivity and the Young modulus after the cycle.
Testing of cycle performance: at 25 ℃, a battery performance testing system (BTS05/10C8D-HP) of the Shenghong electric appliance component electric company Limited is adopted, the discharge capacity of the lithium ion battery at 1C/1C cycle is divided by the first-cycle discharge capacity at the 100 th-cycle discharge capacity, and the 100-cycle retention rate is obtained.
Ion conductivity test after cycling: the ionic conductivity test was performed by the ac impedance method.
Post cycle young modulus test: the test was performed using a nanoindenter tester (Nano introducer XP, Keysight Technologies).
The test results are shown in tables 1 to 5:
TABLE 1
TABLE 2
TABLE 3
TABLE 4
TABLE 5
From table 1, the following points can be seen:
(1) as is clear from examples 1 and 6 to 7, when the young's modulus of the functionalized inorganic particles gradually decreases, the cycle performance of the provided composite lithium negative electrode gradually decreases, and when less than 1GPa, it is difficult to achieve the effects of suppressing penetration of lithium dendrites into the separator and suppressing expansion of the lithium negative electrode; from this, it is understood that when the functionalized inorganic particles of the present invention have a young's modulus of 1GPa or more, the growth of lithium dendrites is suppressed, lithium metal is stabilized, and the swelling effect of the lithium negative electrode in the inorganic particle network is reduced.
(2) From examples 1 and 8 to 9, it can be seen that when the ion conductivity of the functionalized inorganic particles is gradually decreased, the cycle performance of the provided composite lithium negative electrode is also gradually decreased, and when the ion conductivity is less than 10-5At S/cm, it is difficult to achieve the purpose of inhibiting the growth of lithium dendrites; therefore, the functionalized inorganic particles have high ionic conductivity, so that the phenomenon of lithium dendritic crystal growth caused by uneven deposition of lithium ions in the charge-discharge cycle process can be avoided.
(3) As can be seen from example 1 and comparative example 1, in the lithium negative electrode described in comparative example 1, the inorganic particles are not functionalized, and therefore, lithium metal cannot be bonded to the inorganic particles, and thus cannot function as a framework, and the expansion of the lithium negative electrode cannot be suppressed well, so that the cycle performance of the lithium ion battery is significantly reduced.
(4) It can be seen from example 1 and comparative example 2 that the cycle performance of the comparative example using simple lithium metal as the negative electrode is significantly reduced, and as can be seen from fig. 1 and fig. 2, the lithium negative electrode of comparative example 2 has significant lithium dendrite formation on the surface, while example 1 using the composite lithium negative electrode has no significant lithium dendrite formation on the surface after cycling; therefore, the composite lithium negative electrode can inhibit the generation of lithium dendrites, reduce the expansion of the lithium metal negative electrode and improve the cycle performance of the lithium ion battery.
In summary, the present invention provides a composite lithium negative electrode and applications thereof, which can solve the problems of volume expansion and lithium dendrite growth of lithium metal during the cycle process by compounding lithium metal with functionalized inorganic particles.
The above description is only for the specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the protection scope and the disclosure of the present invention.
Claims (10)
1. A composite lithium anode, comprising lithium metal, and functionalized inorganic particles;
the functional group of the functionalized inorganic particle includes any one of a carboxyl group, a carbonyl group, a hydroxyl group, a mercapto group, an aldehyde group, a peptide bond, a carbon-carbon double bond, a carbon-carbon triple bond or a nitro group or a combination of at least two of them.
2. The composite lithium negative electrode according to claim 1, wherein the functionalized inorganic particles have a Young's modulus of 1GPa or more.
3. The composite lithium negative electrode of claim 2, wherein the functionalized inorganic particles have a young's modulus of 1GPa to 6 GPa.
4. The composite lithium anode of claim 3, wherein the functionalized inorganic particles have an ionic conductivity of 10-5S/cm to 10-3S/cm。
5. The composite lithium anode of claim 1, wherein the functionalized inorganic particles have a particle size D50Is 100nm to 600 nm.
6. The composite lithium anode of claim 4, wherein the inorganic particles comprise silicon-based inorganic particles.
7. The composite lithium anode of claim 6, wherein the silicon-based inorganic particles comprise silica and/or LiSixOyWherein x > 0 and y > 0.
8. The composite lithium anode of claim 7, wherein the silicon-based inorganic particles comprise LiSixOyWherein x is more than 0 and less than 1, and y is more than 0 and less than 3.
9. An electrochemical device comprising the composite lithium negative electrode according to any one of claims 1 to 8.
10. An electronic device, characterized in that the electronic device comprises the electrochemical device according to claim 9.
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