CN112201777A - High-energy-density negative electrode material, negative plate comprising same and lithium ion battery - Google Patents
High-energy-density negative electrode material, negative plate comprising same and lithium ion battery Download PDFInfo
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Abstract
The invention provides a high-energy-density negative electrode material, a negative electrode plate and a lithium ion battery, wherein the negative electrode plate comprises the negative electrode material; the mass ratio of the metal carbide nanosheets to the graphite is 1:9-9: 1. The cathode material has high gram capacity and small particle size due to high tap densityNegative electrode sheets prepared after compounding with commercial graphite can achieve high compaction densities, for example when Ti3C2When the proportion of the negative electrode material is 50 wt%, the gram capacity is improved by about 26mAh/g, and the compaction density of the negative electrode sheet is improved by about 0.3g/cm3(ii) a When Ti is present3C2When the proportion of the negative electrode material is 50 wt%, the mass energy density of the lithium ion battery prepared by using the negative electrode material obtained by the invention is improved by about 10.5Wh/Kg, and the volume energy density is improved by about 28.2 Wh/L.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a high-energy-density negative electrode material, a negative electrode plate comprising the negative electrode material and a lithium ion battery.
Background
The lithium ion battery is developed rapidly due to the advantages of long cycle life, environmental friendliness, no memory effect and the like, the application range of the lithium ion battery is gradually expanded from the application of a small-capacity battery in consumer electronics and electric tools to emerging fields such as new energy electric automobiles, electric ships, electric airplanes and robots, and the fields not only require the lithium ion battery to have larger capacity, but also continuously provide higher requirements for the energy density of the lithium ion battery.
The high energy density lithium ion battery can be realized by various technical means, for example, in the aspect of cell design, the energy density of the lithium ion battery can be improved by optimizing the surface density, thickness, porosity, N/P ratio and other electrode sheet parameters of positive and negative electrode sheets, but the energy density which can be improved by design on the basis of the existing material is limited; in the aspect of materials, the cell energy density is improved by developing anode and cathode materials with higher gram capacity and high compaction and developing thinner auxiliary materials such as anode and cathode current collectors, diaphragms, packages and the like, wherein the upgrading and development of anode and cathode active substances are the core of material parts. In contrast, in recent years, the development of negative electrode materials has been rapid, and from conventional graphite-based negative electrodes to silicon-based negative electrodes, tin-based negative electrodes to nanoscale silicon-carbon negative electrodes, these negative electrodes all have very high gram capacities, but all have fatal defects that cannot be overcome, such as short cycle life caused by material pulverization in the cycle process.
Therefore, in order to realize a lithium ion battery with higher energy density, development of a negative electrode material with higher gram capacity and high compaction density is urgently needed.
Disclosure of Invention
The invention aims to provide a high-energy-density negative electrode material, a negative electrode sheet comprising the negative electrode material and a lithium ion battery.
The purpose of the invention is realized by the following technical scheme:
the invention provides a negative electrode material, which is a composite material, wherein the composite material comprises metal carbide nanosheets and graphite; the mass ratio of the metal carbide nanosheets to the graphite is 1:9-9: 1.
According to the invention, the gram capacity of the negative electrode material is 300-450 mAh/g; further, the gram capacity of the negative electrode material is 340-410 mAh/g; illustratively 348, 355, 376, 390, 404mAh/g or any combination of two thereof.
According to the invention, the compacted density of the negative electrode material is 1.5-2.5g/cm3(ii) a Further, the compacted density of the anode material is 1.7-2.1g/cm3Specifically, it may be 1.9g/cm3。
According to the invention, the negative electrode material is in the form of particles, the median particle diameter D of which50Is 3-30 μm.
Wherein at least one dimension of the three-dimensional dimensions of the metal carbide nanosheets is 0.2-1.5 μm.
Wherein the metal carbide nanoplates are selected from Ti2C、Ti3C2TiNbC or (Ti)0.5Nb0.5)2C。
Wherein the graphite has a median particle diameter D50Is 3-30 μm.
As mentioned above, the composite material comprises the metal carbide nanosheets and graphite, the metal carbide nanosheets have the characteristics of high tap density and high gram capacity, and the introduction of the metal carbide nanosheets can improve the compaction density of the negative electrode material; in addition, the graphite has long cycling performance, which can improve the cycling performance on the one hand, and the combination of the graphite and the nano-sheets, particularly the combination of large-particle graphite and small-particle metal carbide nano-sheets, can further improve the compaction density on the other hand.
Specifically, the negative electrode material is a composite material of a metal carbide nanosheet and graphite.
According to the invention, the mass ratio of the metal carbide nanosheets to the graphite is 1:9-9: 1. Specifically, the mass ratio of the two is 1:9, 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, 8:2 or 9: 1.
According to the present invention, the anode material is prepared by the method described below.
The invention also provides a preparation method of the cathode material, which comprises the following steps:
(1) mixing a metal precursor, lithium fluoride and hydrochloric acid, and reacting to prepare a metal carbide;
(2) stripping the metal carbide in the step (1) to obtain a metal carbide nanosheet;
(3) and (3) mixing the metal carbide nanosheets obtained in the step (2) with graphite, and calcining to prepare the composite material of the metal carbide nanosheets and the graphite, namely the negative electrode material.
According to the invention, in the step (1), for example, the lithium fluoride and the hydrochloric acid are mixed, then the metal precursor is mixed with the mixed solution of the lithium fluoride and the hydrochloric acid, and the hydrofluoric acid obtained by the reaction of the lithium fluoride and the hydrochloric acid is used for etching and removing the metal layer in the metal precursor, so that the accordion-shaped metal carbide can be obtained.
According to the invention, in step (1), the molar ratio of lithium fluoride to hydrochloric acid is from 1:2 to 1:4, for example 1: 3.
According to the invention, in step (1), the hydrochloric acid has a concentration of 3 to 8mol/L, such as 6 mol/L.
According to the invention, in the step (1), the mass volume of the mixed solution of the metal precursor, the lithium fluoride and the hydrochloric acid is 1g:8-12mL, namely, 8-12mL of the mixed solution of the lithium fluoride and the hydrochloric acid is added into 1g of the metal precursor.
According to the invention, in step (1), the metal precursor is selected from Ti2AlC、Ti3AlC2TiNbAlC or (Ti)0.5Nb0.5)2AlC。
According to the invention, in step (1), the temperature of the reaction is between 25 and 40 ℃, for example 30 ℃. The reaction time is 1 to 3 days, such as 2 days.
In step (1) of the present invention, a metal precursor (e.g., Ti) is used in the reaction2AlC、Ti3AlC2TiNbAlC or (Ti)0.5Nb0.5)2AlC) is etched away, resulting in an "accordion" like metal carbide, as shown in fig. 1.
The accordion-shaped metal carbide is formed by connecting nano sheets with the length of about 2.5-8 mu m, the width of about 2.5-8 mu m and the thickness of about 2-50nm, namely the metal carbide forming the metal carbide nano sheets is in an accordion shape.
According to the invention, the step (2) further comprises the step of centrifugally washing the obtained metal carbide with deionized water until the pH value is 6-7.
According to the present invention, in the step (2), the peeling is performed, for example, in the presence of deionized water.
According to the invention, in step (2), the stripping is carried out ultrasonically, for example in an ultrasonic instrument with a power of 700W and a frequency of 20 KHz.
According to the invention, in the step (2), the metal carbide nanosheet obtained after stripping is diluted by deionized water, so as to obtain a dispersion liquid of the metal carbide nanosheet.
Illustratively, the stripping is to mix the metal carbide and deionized water at 1g:250-750mL (e.g., 1g:500mL), ultrasonically strip for 3-8h (e.g., 5h), centrifugally separate at 9000r/min, ultrasonically wash to obtain metal carbide nanosheets, and then add deionized water to the metal carbide nanosheets to dilute to obtain a dispersion liquid of the metal carbide nanosheets, wherein the concentration of the dispersion liquid of the metal carbide nanosheets is 5-20mg/g, that is, 1g of the dispersion liquid contains 5-20mg of the metal carbide nanosheets.
According to the invention, in the step (3), the dispersion liquid containing the metal carbide nanosheets obtained in the step (2) is mixed with graphite, the pH is adjusted to be neutral, the mixture is uniformly mixed by ultrasonic waves, precipitates are obtained by centrifugation, the dried products are dried in vacuum, and the dried products are subjected to N2Calcining in the atmosphere to prepare the composite material of the metal carbide nanosheet and the graphite, namely the negative electrode material.
Wherein the vacuum drying is carried out under the condition of normal temperature, and the moisture after drying is less than 150 ppm.
According to the present invention, in step (3), the temperature of the calcination is 800-.
According to the invention, in the step (3), the mass ratio of the metal carbide nanosheets to the graphite is 1:9-9: 1.
The invention also provides a negative plate which comprises the negative electrode material.
According to the present invention, the negative electrode sheet includes a negative electrode active material layer including the above-described negative electrode material.
According to the present invention, the anode active material layer further includes a conductive agent and a binder.
According to the invention, the mass percentage of each component in the negative electrode active material layer is as follows: 70-99 wt% of negative electrode material, 0.5-15 wt% of conductive agent and 0.5-15 wt% of binder.
Preferably, the negative electrode active material layer comprises the following components in percentage by mass: 80-98 wt% of negative electrode material, 1-10 wt% of conductive agent and 1-10 wt% of binder.
Wherein the conductive agent is at least one selected from conductive carbon black, acetylene black, Ketjen black, conductive graphite, conductive carbon fiber, carbon nanotube, metal powder and carbon fiber.
Wherein the binder is selected from at least one of sodium carboxymethylcellulose, styrene-butadiene latex, polytetrafluoroethylene and polyethylene oxide.
The invention also provides a lithium ion battery which comprises the negative plate.
According to the invention, the lithium ion battery is a wound lithium ion battery or a laminated lithium ion battery.
The invention has the beneficial effects that:
the invention provides a high-energy-density negative electrode material, a negative electrode sheet comprising the negative electrode material and a lithium ion battery, wherein the gram capacity of the negative electrode material is high, and the high-compaction density can be realized by the negative electrode sheet prepared by compounding the negative electrode material with commercial graphite due to high tap density and small particle size, such as Ti3C2When the proportion of the negative electrode material is 50 wt%, the gram capacity is improved by about 26mAh/g, and the compaction density of the negative electrode sheet is improved by about 0.3g/cm3(ii) a When Ti is present3C2When the proportion of the negative electrode material is 50 wt%, the mass energy density of the lithium ion battery prepared by using the negative electrode material obtained by the invention is improved by about 10.5Wh/Kg, and the volume energy density is improved by about 28.2 Wh/L.
Drawings
FIG. 1 is an SEM image of "accordion" shaped metal carbide as described in example 1.
Fig. 2 is an SEM image of the metal carbide nanoplates described in example 1.
Fig. 3 is an SEM image of the negative electrode material after the metal carbide and graphite were compounded in example 1.
Detailed Description
The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1
(1) Preparation of metal carbide/graphite composite negative electrode material
Mixing lithium fluoride and hydrochloric acid with the concentration of 6mol/L according to the molar ratio of 1:3, and magnetically stirring for about 10 min;
② Ti3AlC2Mixing with the solution obtained in the step (i) at a ratio of 1g to 10mL, and standing at 30 ℃ for 3 days to obtain accordion-shaped Ti3C2Particles;
③ mixing the obtained Ti3C2The particles were washed centrifugally with deionized water to pH 6;
fourthly, the sediment obtained in the third step is mixed with deionized water with the volume of 1g:500mL, ultrasonic stripping is carried out for 5h (700W, 20KHz), centrifugal separation is carried out at 9000r/min, washing is repeated for 6 times, and washed Ti is obtained3C2Nanosheets, adding deionized water thereto for dilution to obtain Ti3C2A dispersion of nanoplatelets having a concentration of about 10 mg/g;
fifthly, mixing the dispersion liquid obtained in the step IV with graphite, wherein Ti is3C2The mass ratio of the nano sheets to the graphite is 1:9, the pH is adjusted to be 7, the nano sheets and the graphite are uniformly mixed by ultrasonic for 1h, a precipitate is obtained by centrifugation, and the precipitate is dried in vacuum for 48h under the condition of normal temperature to remove water;
drying the product in N2Calcining for 4h at 1000 ℃ in the atmosphere to obtain the composite material of the metal carbide nanosheet and the graphite.
(2) Preparation of negative plate
The synthesized composite material of the metal carbide nanosheet and graphite is used as a negative electrode material, a binder (SBR) and a conductive agent (conductive carbon black) are mixed according to a mass ratio of 95:3:2, water is used as a solvent, the mixture is uniformly stirred to prepare slurry, the slurry is uniformly coated on two sides of a copper foil, and the copper foil is dried, rolled and punched into small pieces.
(3) Preparation of positive plate
Mixing the positive electrode material lithium iron phosphate, a conductive agent (conductive carbon black) and a binder (PVDF) according to the mass ratio of 95:3:2, using N-methyl pyrrolidone as a solvent, uniformly stirring to prepare slurry, uniformly coating the slurry on two sides of an aluminum foil, drying, rolling and punching into small pieces.
(4) Assembly of lithium ion batteries
Forming a bare cell by laminating a positive plate, a negative plate and a diaphragm according to a Z shape, welding an aluminum tab and a copper nickel-plated tab, packaging an aluminum-plastic film, baking for 24 hours in vacuum, injecting liquid, and performing chemical aging to obtain the soft package lithium ion battery cell (length multiplied by width multiplied by thickness is 230mm multiplied by 165mm multiplied by 7 mm). Wherein, the electrolyte adopts lithium hexafluorophosphate electrolyte containing 1mol/L, and the solvent is a mixed solvent of ethylene carbonate/dimethyl carbonate/1, 2 propylene carbonate 1:1:1 (volume ratio).
FIG. 1 is an SEM photograph of "accordion" like titanium carbide as an intermediate product obtained in step (1) of example 1, and as can be seen from FIG. 1, "accordion" like titanium carbide was produced. Fig. 2 is an SEM image of titanium carbide nanoplates prepared in example 1. As can be seen in FIG. 2, the morphology of the titanium carbide is a nanosheet structure, the length of the nanosheet is 0.2-1.5 μm, and the width of the nanosheet is 0.2-1.5 μm. FIG. 3 is an SEM photograph of a composite material formed by compositing titanium carbide and graphite in example 1. As can be seen in FIG. 3, titanium carbide and graphite can be well compounded to prepare the composite material.
Example 2
Compounding the metal carbide nanosheets and the graphite in a mass ratio of 1:1 to obtain corresponding negative electrode materials, wherein other conditions are consistent with those in example 1.
Example 3
Compounding the metal carbide nanosheets and the graphite in a mass ratio of 9:1 to obtain corresponding negative electrode materials, wherein other conditions are consistent with those in example 1.
Comparative example 1
Compounding the metal carbide nanosheets and graphite in a mass ratio of 0:10, namely only containing graphite to obtain a corresponding negative electrode material, wherein other conditions are consistent with those of example 1.
Comparative example 2
Compounding the metal carbide nanosheets and the graphite in a mass ratio of 10:0, namely only containing the metal carbide nanosheets to obtain a corresponding negative electrode material, wherein other conditions are consistent with those in example 1.
The lithium ion battery cells prepared in the above examples and comparative examples were subjected to performance tests, the test procedures were as follows:
1) mass energy density test:
the completed cell was weighed (unit g) with an electronic balance. The mass Energy Density (ED, unit Wh/Kg) is the sorting discharge Energy value (Wh)/battery mass × 1000, and the results are reported in table 1.
2) Volumetric energy density test:
the thickness (unit mm) of the battery was measured using a 600g PPG thickness gauge, and the length and width (unit mm) were determined based on the model of the battery and were regarded as fixed values. The volumetric Energy Density (ED, unit Wh/L) is the sort discharge Energy value (Wh)/cell thickness/cell length/cell width × 1000, and the results are reported in table 1.
3) Normal temperature cycle test at 25 deg.C
Placing the battery in an environment of (25 +/-3) DEG C, standing for 3 hours, discharging the battery to 2.2V according to a constant current of 1C when the battery core body reaches (25 +/-3) DEG C, then charging to 3.65V with a constant current and a constant voltage of 1C and a cut-off current of 0.05C, then discharging to 2.2V with 1C, recording initial capacity Q0When the cycle reaches the required number, the previous discharge capacity is used as the capacity Q of the battery2The capacity retention (%) was calculated, and the results are reported in table 1. The calculation formula used therein is as follows: capacity retention (%) ═ Q2/Q0×100％。
4) High temperature cycle test at 45 deg.C
Placing the battery in an environment of (45 +/-3) DEG C, standing for 3 hours, discharging the battery to 2.2V according to a constant current of 1C when the battery core body reaches (45 +/-3) DEG C, then charging to 3.65V with a constant current and a constant voltage of 1C and a cut-off current of 0.05C, then discharging to 2.2V with 1C, recording initial capacity Q0And cycling in such a manner that when the cycle reaches the required number of times, the previous discharge capacity is taken as the capacity Q of the battery3The capacity retention (%) was calculated, and the results are reported in table 1. The calculation formula used therein is as follows: capacity retention (%) ═ Q3/Q0×100％。
Table 1 composition and performance testing of lithium ion batteries of examples and comparative examples
Compared with the comparative example 1, the mass energy density and the volume energy density of the battery core using the negative electrode material are obviously improved in the examples 1,2 and 3, the cycle performance of the example 3 is poor, the example 1 is better, and the example 2 is the second time; compared with the comparative example 2, the cycle performance of the negative electrode material compounded with graphite in the example is obviously improved. In conclusion, the negative electrode material obtained by compounding the metal carbide nanosheets/graphite prepared by the method has the advantages that the mass energy density and the volume energy density can be obviously improved on the premise of ensuring the good cycle life of the lithium ion battery cell, and the application prospect is wide.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. An anode material, wherein the anode material is a composite material comprising metal carbide nanoplates and graphite; the mass ratio of the metal carbide nanosheets to the graphite is 1:9-9: 1.
2. The anode material according to claim 1, wherein the gram capacity of the anode material is 300-450 mAh/g; and/or the presence of a gas in the gas,
the compacted density of the negative electrode material is 1.5-2.5g/cm3(ii) a And/or the presence of a gas in the gas,
the median particle diameter D of the negative electrode material50Is 3-30 μm.
3. The negative electrode material of claim 1 or 2, wherein at least one of the three-dimensional dimensions of the metal carbide nanoplates is 0.2-1.5 μ ι η; and/or the presence of a gas in the gas,
the metal carbide nanosheets being selected from Ti2C、Ti3C2TiNbC or (Ti)0.5Nb0.5)2C; and/or the presence of a gas in the gas,
median particle diameter D of the graphite50Is 3-30 μm.
4. The anode material according to any one of claims 1 to 3, wherein the metal carbide forming the metal carbide nanosheets is accordion-shaped.
5. A method of preparing an anode material, the method comprising the steps of:
(1) mixing a metal precursor, lithium fluoride and hydrochloric acid, and reacting to prepare a metal carbide;
(2) stripping the metal carbide in the step (1) to obtain a metal carbide nanosheet;
(3) and (3) mixing the metal carbide nanosheets obtained in the step (2) with graphite, and calcining to prepare the composite material of the metal carbide nanosheets and the graphite, namely the negative electrode material.
6. The production method according to claim 5, wherein in the step (1), the molar ratio of the lithium fluoride to the hydrochloric acid is 1:2 to 1: 4; and/or the presence of a gas in the gas,
in the step (1), the mass volume of the mixed solution of the metal precursor, the lithium fluoride and the hydrochloric acid is 1g:8-12 mL; and/or the presence of a gas in the gas,
in the step (1), the metal precursor is selected from Ti2AlC、Ti3AlC2TiNbAlC or (Ti)0.5Nb0.5)2AlC; and/or the presence of a gas in the gas,
in the step (1), the reaction temperature is 25-40 ℃, and the reaction time is 1-3 days; and/or the presence of a gas in the gas,
in the step (1), the metal carbide is formed by connecting nanosheets with the length of about 2.5-8 μm, the width of about 2.5-8 μm and the thickness of about 2-50 nm; and/or the presence of a gas in the gas,
in the step (2), before the stripping, the obtained metal carbide is centrifugally washed by deionized water until the pH value is 6-7; and/or the presence of a gas in the gas,
in the step (2), the stripping is carried out in the presence of deionized water; and/or the presence of a gas in the gas,
in the step (2), the stripped metal carbide nanosheets are diluted by deionized water to obtain dispersion liquid of the metal carbide nanosheets; and/or the presence of a gas in the gas,
in the step (3), the calcining temperature is 800-1200 ℃, and the calcining time is 3-6 hours; and/or the presence of a gas in the gas,
in the step (3), the mass ratio of the metal carbide nanosheets to the graphite is 1:9-9: 1.
7. A negative electrode material produced by the production method according to any one of claims 4 to 6.
8. A negative electrode sheet, wherein the negative electrode sheet comprises the negative electrode material according to any one of claims 1 to 3 or 7.
9. The negative electrode sheet according to claim 8, comprising a negative electrode active material layer;
wherein the anode active material layer includes the anode material according to any one of claims 1 to 3 and 7; and/or the presence of a gas in the gas,
the negative electrode active material layer comprises the negative electrode material, the conductive agent and the binder, wherein the negative electrode active material layer comprises the following components in percentage by mass: 70-99 wt% of negative electrode material, 0.5-15 wt% of conductive agent and 0.5-15 wt% of binder.
10. A lithium ion battery comprising the negative electrode sheet of claim 8 or 9.
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| WO2019126549A1 (en) * | 2017-12-22 | 2019-06-27 | Zenlabs Energy, Inc. | Electrodes with silicon oxide active materials for lithium ion cells achieving high capacity, high energy density and long cycle life performance |
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