CN116364941A - Fast-charging negative electrode and application thereof in non-anode battery - Google Patents
Fast-charging negative electrode and application thereof in non-anode battery Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 claims abstract description 74
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 69
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 23
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 23
- 239000011734 sodium Substances 0.000 claims abstract description 23
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 9
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 6
- 238000000137 annealing Methods 0.000 claims description 28
- 239000011888 foil Substances 0.000 claims description 19
- 238000005097 cold rolling Methods 0.000 claims description 18
- 238000005098 hot rolling Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims 1
- 210000001787 dendrite Anatomy 0.000 abstract description 22
- 238000002360 preparation method Methods 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 13
- 230000014759 maintenance of location Effects 0.000 abstract description 9
- 230000005764 inhibitory process Effects 0.000 abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 30
- 239000010949 copper Substances 0.000 description 21
- 230000008021 deposition Effects 0.000 description 18
- 229910052786 argon Inorganic materials 0.000 description 15
- 239000000956 alloy Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 229910045601 alloy Inorganic materials 0.000 description 13
- 239000011701 zinc Substances 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 238000005266 casting Methods 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000011889 copper foil Substances 0.000 description 6
- 229910001297 Zn alloy Inorganic materials 0.000 description 5
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
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- 239000006258 conductive agent Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000011883 electrode binding agent Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910002535 CuZn Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
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- -1 lithium hexafluorophosphate Chemical group 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 230000002195 synergetic effect Effects 0.000 description 2
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 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
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
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- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/40—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling foils which present special problems, e.g. because of thinness
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- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
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- C22C9/02—Alloys based on copper with tin as the next major constituent
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- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
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- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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- H01M10/052—Li-accumulators
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- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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Abstract
The invention provides a fast-charge anode with high lithium/sodium affinity and high conductivity, wherein the conductivity is not less than 10mS/m; the component is Cu x M y A z Wherein M is three or more of Zn, ni, mn, sn, pb, mg, al, ga, ge, co, fe, V, cr, ti elements; a is one or more than one of B, si, P, se elements. The fast-charge anode provided by the invention can improve the affinity between the anode and lithium/sodium, so that the lithium/sodium can be uniformly deposited under high current density, and dendrite generation is inhibited even at 100mA/cm 2 The preparation method still has better dendrite inhibition effect under the ultra-high current density, can greatly improve the fast charge capacity retention rate of the non-anode battery, has simpler preparation method and lower comprehensive preparation cost, and is suitable for popularization and application.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a fast-charge negative electrode and application thereof in a battery without an anode.
Background
In order to increase the energy density of the battery, researchers have developed a novel non-anode battery in recent years, and the energy density of the battery has been greatly increased by not using a negative electrode active material. The principle of the technology is that lithium in a positive electrode material is deposited on a negative electrode current collector through formation charging. However, the non-anode battery has problems such as poor quick charge performance. The main reason is that: the current commonly used negative current collector is copper foil, but lithium is difficult to be uniformly deposited on the surface of the copper foil in the charging process due to poor affinity between the copper foil and lithium, and a large amount of lithium dendrites and dead lithium can be formed in the working process of the battery, so that the internal resistance of the battery is increased, and the quick charging performance of the battery is affected. Especially in the case of high-rate charging, dendrites can grow rapidly, fracture forms dead lithium, and the battery capacity is greatly attenuated, so that the battery has poor rapid charging performance.
Techniques for improving the lithium deposition effect include using a three-dimensional current collector, forming a lithium-philic layer on the surface of the current collector by modification, using an alloy current collector with good lithium affinity, and the like.
Chinese patent CN202110119058.8 discloses a method for regulating and controlling thermal oxidation of the surface of a lithium metal negative electrode collector to improve cycle life, which comprises sequentially degreasing and pickling the metal collector, forming a three-dimensional structure on the surface of the metal collector, and performing thermal oxidation treatment on the three-dimensional collector surface to change the lithium affinity of the negative electrode collector surface, thereby improving the deposition uniformity of lithium metal on the surface of the collector at 1mA/cm 2 And the lithium dendrite growth is effectively inhibited and the long cycle life of the battery is prolonged under the charge and discharge rate. However, since the oxide layer has poor conductivity, the polarization of the negative electrode is greatly increased under high current density charging, and lithium deposition uniformity is deteriorated, so that it is difficult to suppress lithium dendrite growth.
The Chinese patent CN201810219640.X discloses a copper-zinc alloy current collector for inhibiting lithium dendrite, a layer of copper-zinc alloy with the thickness of 10 nm-1 μm is covered on a conventional current collector, and the atomic content of zinc in the copper-zinc alloy is 1% -5%. Compared with the conventional current collector, the copper-zinc alloy current collector can provide more active sites for metal lithium deposition, and the current density is 0.5mA/cm by using blue electricity for deposition/dissolution experiments 2 After 1000 hours of circulation, the copper zinc alloy cathode still keeps smaller voltage hysteresis. However, since the lithium philic effect of zinc is limited, the lithium deposition effect of high current density charging cannot be improved.
Chinese patent CN202210764790.5 discloses a high-entropy alloy current collector, which uses the high-entropy alloy current collector to replace the existing copper foil current collector, and can effectively regulate and control lithium deposition while meeting the requirements related to the non-anode lithium metal battery, thereby reducing or avoiding the formation of lithium dendrites and overcoming the defects existing in the existing non-anode lithium metal. At charge and discharge rates of 0.1C and 1C, the coulombic efficiency, initial discharge capacity, and capacity retention rate of the anodeless lithium metal battery can be improved. However, since the high-entropy alloy contains a large amount of components with higher resistivity, the resistivity is about two orders of magnitude higher than that of pure copper, the polarization of the negative electrode is greatly increased under the condition of high current density charging, the uniformity of lithium deposition is poor, and the growth of lithium dendrites is difficult to inhibit.
Disclosure of Invention
Aiming at the problems of uneven lithium/sodium deposition and easy generation of dendrite and dead lithium/sodium in the high current density existing in the prior art, the invention provides a fast-charging anode with high lithium/sodium affinity and high conductivity. The invention can improve the affinity between the cathode and the lithium/sodium, ensure that the lithium/sodium can be uniformly deposited under high current density, inhibit the generation of dendrite even at 100mA/cm 2 The high-voltage battery has better dendrite inhibition effect under the ultra-high current density, and can greatly improve the fast charge capacity retention rate of the non-anode battery.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a fast-charging anode is an alloy containing Cu x M y A z Wherein M is three or more of Zn, ni, mn, sn, pb, mg, al, ga, ge, co, fe, V, cr, ti and other elements; a is one or more than one of B, si, P, se and other elements; x, y and z are the total mole numbers of elements Cu, M and A in the component, and x, y and z satisfy the following relation in terms of x+y+z=1: x is more than or equal to 0.66 and less than or equal to 0.89,0.06, y is more than or equal to 0.24,0.04, z is more than or equal to 0.15, and z is more than or equal to y. The conductivity of the fast-charge anode is not less than 10mS/m and 100mA/cm 2 The specific charge retention rate is not less than 50%, and the coulomb efficiency is more than 98%.
In the fast-charge anode, cu has the effect of improving the conductivity of the anode, but Cu has poor lithium/sodium affinity, so that if the content of Cu is too high, the lithium/sodium affinity of the anode is poor, and if the content of Cu is too low, the conductivity of the anode is low; the function of M is to improve the uniformity and stability of the alloy of the negative electrode, but M also has the problem of poor lithium/sodium affinity, so that if the content of M is too high, the lithium/sodium affinity of the negative electrode is poor, and if the content of M is too low, the uniformity and stability of the negative electrode are poor; the effect of a is to increase the lithium/sodium affinity of the negative electrode, but the conductivity of a is low, so that if the content is too high, the conductivity of the negative electrode is lowered, and if the content is too low, the lithium/sodium affinity of the negative electrode is poor. By accurately regulating and controlling the contents of the Cu, M and A components, the Cu, M and A components can play a synergistic role within the technical scheme provided by the invention, so that the negative electrode has high lithium affinity and high conductivity.
Preferably, the molar ratio of the elements in M is equal.
Preferably, the molar ratio of the elements in a is equal.
Further preferably, the M may be divided into two parts M1 and M2, wherein M1 is Zn, sn, pb, al, mg, ga, ge, two or more of elements; m2 is zero or more in Ni, mn, co, fe, V, cr, ti element. M1 and M2 are classified according to their lithium/sodium affinity, M1 being better than M2.
Further preferably, the elemental species of M1 is greater than the elemental species of M2.
Further preferably, A is an element, and z is 0.04.ltoreq.z.ltoreq.0.1.
Further preferably, the A is two elements, and z is more preferably more than or equal to 0.06 and less than or equal to 0.12.
Further preferably, A is three or more elements, and z is 0.07.ltoreq.z.ltoreq.0.15.
Further preferably, the thickness of the fast-charge anode is 4-50 um. Further, the thickness of the fast-charge anode is more preferably 5-25 um.
The invention also provides a preparation method of the quick-charge anode, which comprises the following steps:
step 1: elemental powders of elements Cu, M and A are uniformly mixed according to the element proportion in the components, melted and cast into a block-shaped blank;
step 2: heating the block-shaped blank, hot rolling, cooling, and cold rolling to obtain a plate;
step 3: annealing the sheet material, and then performing secondary cold rolling to prepare a foil material;
step 4: and annealing the foil to remove stress to obtain the fast-charging anode.
In the preparation method, the heat preservation is carried out for 2 to 8 hours at 900 to 1200 ℃ before the hot rolling in the step 2.
In the preparation method, in the steps 3 and 4, annealing is carried out under the protection of nitrogen, argon and other gases, the annealing temperature is 400-600 ℃, and the heat preservation time is 2-6 h.
On the basis of the above, the invention also provides an anode-free battery, which comprises the fast-charge anode as an anode current collector, and can be an anode-free lithium battery or an anode-free sodium battery according to the selection of anode materials and electrolytes in the battery.
The main technical ideas of the invention are as follows:
so-called quick charging, i.e. quick completion of charging in a relatively short period of time, generally requires a charging rate of 4C or more, or a charging current density of 10mA/cm 2 The above. Because the affinity between the copper current collector adopted by the anode-free battery and lithium is poor, lithium deposition is uneven in the working process, dendrite and dead lithium are extremely easy to generate, and the dendrite and dead lithium are positively correlated with the charging current density, namely, the larger the charging current density is, the worse the lithium deposition uniformity is. The prior technology for improving the uniformity of lithium deposition mainly has the following two defects:
first, although the high conductivity of the negative electrode is maintained, the improvement effect on the lithium philicity of the negative electrode is limited, the lithium philicity of the lithium philic component (e.g., zn) is not very good, or the lithium philic component is relatively small, and only the uniformity of lithium deposition at a medium-small current density can be improved, but the uniformity of lithium deposition at a large current density cannot be improved. At high current density, li + Greatly improves the flux of a large amount of Li + The lithium needs to be deposited on the surface of the negative electrode rapidly, and if the lithium affinity of the negative electrode substrate is poor or the lithium-philic active sites are few, the lithium deposition is uneven.
Secondly, although the lithium-philic effect of the cathode is well improved, the conductivity of the cathode is greatly reduced, the electrode polarization is inversely related to the conductivity of the electrode, and is positively related to the current density, and the charge under the high current density can lead the polarization of the cathode with low conductivity to be largeIncrease in width, negative electrode surface Li + The current is disturbed, the lithium deposition uniformity is deteriorated, the charging voltage is rapidly increased to reach the charging cut-off voltage, and the battery capacity is greatly attenuated.
Through researches on various materials and combinations thereof, the lithium affinity of the negative electrode is improved by introducing proper lithium-philic components into the negative electrode, the proportion of each component in the negative electrode is regulated and controlled, the conductivity of the negative electrode is improved, and finally the fast-charging negative electrode with high lithium affinity and high conductivity is prepared. The prior art does not have the technical teaching of the design idea.
Compared with the prior art, the invention has at least the following beneficial effects:
1) According to the invention, the component A with good affinity with lithium/sodium is introduced into the negative electrode, so that the affinity between the negative electrode and lithium/sodium can be improved, lithium/sodium is uniformly deposited on the surface of a negative electrode current collector, and generation of lithium/sodium dendrite is inhibited;
2) The invention can realize the synergistic effect of the three components Cu, M and A by accurately regulating and controlling the contents of the three components Cu, M and A within the technical proposal provided by the invention, so that the cathode has high lithium affinity and high conductivity at the same time, even up to 100mA/cm 2 The high-voltage battery has better dendrite inhibition effect under the ultra-high current density, and can greatly improve the fast charge capacity retention rate of the non-anode battery;
3) The preparation method is simple, has low comprehensive cost and can be used for large-scale industrial production.
Drawings
FIG. 1 is a graph of specific charge capacity at different current densities for example 1 and comparative example 1;
FIG. 2 is 100mA/cm for example 1 and comparative example 1 2 Current density charged negative SEM images.
Detailed Description
For a better understanding of the present invention, the following examples are set forth to illustrate the invention further, but are not to be construed as limiting the invention.
Example 1
(1) Preparation of fast-charging negative electrode
Composition of negative electrodeIs Cu 0.8 Mg 0.04 Al 0.04 Sn 0.04 Si 0.04 Se 0.04 ：
Step 1: uniformly mixing Cu, mg, al, sn, si, se powder according to the element proportion of the components, melting, and casting into a block-shaped blank;
step 2: heating the blank to 1000 ℃, preserving heat for 5 hours, hot rolling, and cold rolling after cooling to prepare a plate;
step 3: annealing the plate at 500 ℃ under the protection of argon, preserving heat for 4 hours, and then performing secondary cold rolling to prepare a foil with the thickness of 15 um;
step 4: and (3) annealing the foil to remove stress under the protection of argon, wherein the annealing temperature is 550 ℃, and preserving heat for 3 hours to obtain the fast-charging anode. Slicing the negative electrode to prepare a negative electrode plate.
(2) Preparation of the Positive electrode
The positive electrode active material adopts lithium cobaltate, the positive electrode conductive agent adopts SP, the positive electrode binder adopts PVDF, and the positive electrode current collector adopts aluminum foil. The mass ratio of the positive electrode active material, the positive electrode conductive agent and the positive electrode binder is 97:1.5:1.5. And preparing the positive electrode active material, the positive electrode conductive agent and the positive electrode binder into slurry, coating the slurry on a positive electrode current collector, and drying, rolling and die-cutting the slurry to prepare the positive electrode plate.
(3) Battery preparation
The CR2032 button type non-anode battery is prepared by adopting the negative plate and the positive plate prepared by the steps. The method comprises the following steps: the negative electrode shell, the negative electrode plate, the diaphragm (50 uL of electrolyte is dripped when the diaphragm is placed), the positive electrode plate, the gasket, the elastic sheet and the positive electrode shell are sequentially stacked and then fastened. The diaphragm adopts PE/PP double-layer diaphragm, and the electrolyte is lithium hexafluorophosphate with the concentration of 1 mol/L.
Example 2
(1) Preparation of fast-charging negative electrode
The negative electrode comprises Cu 0.66 Zn 0.05 Al 0.05 Ge 0.05 Ni 0.05 V 0.05 P 0.03 Si 0.03 Se 0.03 ：
Step 1: uniformly mixing Cu, zn, al, ge, ni, V, P, si, se powder according to the proportion of elements in the components, melting, and casting into a block-shaped blank;
step 2: heating the blank to 900 ℃, preserving heat for 8 hours, hot rolling, and cold rolling after cooling to prepare a plate;
step 3: annealing the plate at 400 ℃ under the protection of argon, preserving heat for 6 hours, and then performing secondary cold rolling to prepare a foil with the thickness of 25 um;
step 4: and (3) annealing the foil to remove stress under the protection of argon, wherein the annealing temperature is 450 ℃, and preserving heat for 6 hours to obtain the fast-charging anode. Slicing the negative electrode to prepare a negative electrode plate.
(2) Positive electrode and battery preparation
Positive electrode sheets and batteries were prepared as in example 1.
Example 3
(1) Preparation of fast-charging negative electrode
The negative electrode comprises Cu 0.73 Mg 0.03 Al 0.03 Zn 0.03 Sn 0.03 Ni 0.03 Co 0.03 P 0.03 Si 0.03 Se 0.03 ：
Step 1: uniformly mixing Cu, mg, al, zn, sn, ni, co, P, si, se powder according to the proportion of elements in the components, melting, and casting into a block-shaped blank;
step 2: heating the blank to 1000 ℃, preserving heat for 5 hours, hot rolling, and cold rolling after cooling to prepare a plate;
step 3: annealing the plate at 500 ℃ under the protection of argon, preserving heat for 3 hours, and then performing secondary cold rolling to prepare a foil with the thickness of 5 um;
step 4: and (3) annealing the foil to remove stress under the protection of argon, wherein the annealing temperature is 550 ℃, and preserving heat for 3 hours to obtain the fast-charging anode. Slicing the negative electrode to prepare a negative electrode plate.
(2) Positive electrode and battery preparation
Positive electrode sheets and batteries were prepared as in example 1.
Example 4
(1) Preparation of fast-charging negative electrode
The negative electrode comprises Cu 0.89 Ge 0.015 Sn 0.015 Al 0.015 Co 0.015 P 0.025 Se 0.025 ：
Step 1: uniformly mixing Cu, ge, sn, al, co, P, se powder according to the proportion of elements in the components, melting, and casting into a block-shaped blank;
step 2: heating the blank to 1200 ℃, preserving heat for 2 hours, hot rolling, and cold rolling after cooling to prepare a plate;
step 3: annealing the plate at 600 ℃ under the protection of argon, preserving heat for 2 hours, and then performing secondary cold rolling to prepare a foil with the thickness of 5 um;
step 4: and (3) annealing the foil to remove stress under the protection of argon, wherein the annealing temperature is 600 ℃, and preserving heat for 2 hours to obtain the fast-charging anode. Slicing the negative electrode to prepare a negative electrode plate.
(2) Positive electrode and battery preparation
Positive electrode sheets and batteries were prepared as in example 1, except that the positive electrode material used sodium ferronickel manganate and the electrolyte used sodium hexafluorophosphate.
Comparative example 1
A 10um thick pure copper foil was cut into a negative electrode sheet, and a positive electrode sheet and a battery were prepared as in example 1.
Comparative example 2
(1) Preparation of negative electrode
The negative electrode comprises CuZn alloy, and the Zn content is 5wt%:
step 1: uniformly mixing Cu and Zn powder according to the element proportion in the components, melting, and casting into a block-shaped blank;
step 2: heating the blank to 1000 ℃, preserving heat for 5 hours, hot rolling, and cold rolling after cooling to prepare a plate;
step 3: annealing the plate at 500 ℃ under the protection of argon, preserving heat for 4 hours, and then performing secondary cold rolling to prepare a foil with the thickness of 15 um;
step 4: and (3) annealing the foil to remove stress under the protection of argon, wherein the annealing temperature is 550 ℃, and preserving heat for 3 hours to obtain the fast-charging anode. Slicing the negative electrode to prepare a negative electrode plate.
(2) Positive electrode and battery preparation
Positive electrode sheets and batteries were prepared as in example 1.
Comparative example 3
(1) Preparation of negative electrode
The negative electrode comprises Cu 0.2 Fe 0.2 Mg 0.2 Mn 0.2 Si 0.2 High entropy alloy:
step 1: uniformly mixing Cu, fe, mg, mn, si powder according to the proportion of elements in the components, melting, and casting into a block-shaped blank;
step 2: heating the blank to 1000 ℃, preserving heat for 5 hours, hot rolling, and cold rolling after cooling to prepare a plate;
step 3: annealing the plate at 500 ℃ under the protection of argon, preserving heat for 4 hours, and then performing secondary cold rolling to prepare a foil with the thickness of 15 um;
step 4: and (3) annealing the foil to remove stress under the protection of argon, wherein the annealing temperature is 550 ℃, and preserving heat for 3 hours to obtain the fast-charging anode. Slicing the negative electrode to prepare a negative electrode plate.
(2) Positive electrode and battery preparation
Positive electrode sheets and batteries were prepared as in example 1.
Comparative example 4
(1) Preparation of negative electrode
The negative electrode comprises CuSnCrZnMgAlSiP alloy, wherein the content of each component is Cu 96.78wt%, sn1.5wt%, cr 0.3wt%, zn 0.12wt%, mg 0.25wt%, al 0.35wt%, si 0.55wt% and P0.15 wt%:
step 1: uniformly mixing Cu, sn, cr, zn, mg, al, si, P powder according to the proportion of elements in the components, melting, and casting into a block-shaped blank;
step 2: heating the blank to 1000 ℃, preserving heat for 5 hours, hot rolling, and cold rolling after cooling to prepare a plate;
step 3: annealing the plate at 500 ℃ under the protection of argon, preserving heat for 4 hours, and then performing secondary cold rolling to prepare a foil with the thickness of 15 um;
step 4: and (3) annealing the foil to remove stress under the protection of argon, wherein the annealing temperature is 550 ℃, and preserving heat for 3 hours to obtain the fast-charging anode. Slicing the negative electrode to prepare a negative electrode plate.
(2) Positive electrode and battery preparation
Positive electrode sheets and batteries were prepared as in example 1.
Performance testing
The conductivities of the cathodes prepared in examples 1 to 4 and comparative examples 1 to 4 were measured, and the results are shown in table 1.
Table 1 conductivity test data sheet
CR2032 button cells prepared in examples 1 to 4 and comparative examples 1 to 4 were each used at 1mA/cm 2 、10mA/cm 2 、100mA/cm 2 The charging and discharging voltage ranges of examples 1 to 3 and comparative examples 1 to 4 are 2.75 to 4.3V, and the charging and discharging voltage ranges of example 4 are 1.5 to 4.1V, and the test results are shown in FIG. 1, FIG. 2, table 2 and Table 3.
Wherein, 100mA/cm 2 Specific charge capacity retention = 100mA/cm 2 Specific charge/1 mA/cm 2 The specific charge capacity is 100%.
Table 2 table of test data for different current densities
TABLE 3 100mA/cm 2 Charge-discharge test data table
As can be seen from the data in fig. 1, table 2 and table 3, the batteries obtained in examples 1 to 4 all have good quick-charge performance. Examples 1 to 4 were charged for only about 50 seconds to a capacity of 50% or more, and the coulombic efficiency was more than 98%. The main reason is that: according to the embodiment, the fast charge cathode provided by the invention is adopted, and the Cu, M and A components can play a role in synergism to induce uniform deposition of lithium/sodium and inhibit generation of dendrite, so that the fast charge performance of the battery is greatly improved.
As can be seen from fig. 2, the lithium deposited on the negative electrode of example 1 has a flat block shape, and has good uniformity and almost no dendrite; while the negative electrode of comparative example 1 was in a fine dendrite shape, dendrite was distributed over the surface of the negative electrode. Indicating that the invention is at 100mA/cm 2 Can still improve the deposition uniformity of lithium and inhibit dendrite growth under the ultra-high current density.
The negative electrode of comparative example 1 adopts pure copper foil, has poor lithium affinity, forms a large amount of dendrites and dead lithium in the charge and discharge process (see fig. 2), causes the increase of polarization of the negative electrode, rapidly touches the charge and discharge cut-off voltage, greatly attenuates the battery capacity, and is 100mA/cm 2 Almost no charge and discharge can be performed at the current density, and the quick charge performance is extremely poor.
The negative electrode of comparative example 2 was made of CuZn alloy having Zn content of 5wt% and high conductivity, but the quick charge property was poor due to poor lithium-philic effect of Zn at 100mA/cm 2 The charge capacity retention at current density of (2) was only 20.5%, the coulombic efficiency was only 12.6%, much lower than in the examples.
The high-entropy alloy material is a new material developed in recent years, wherein a lithium-philic element can be added to improve the lithium-philic effect of the material, but in order to maintain the high-entropy state and uniformity of the material, the molar ratio content of all elements must be equal, and the addition of a large amount of low-conductivity elements can cause the conductivity of the high-entropy alloy to be greatly reduced. The negative electrode of comparative example 3 was prepared with Cu as the component 0.2 Fe 0.2 Mg 0.2 Mn 0.2 Si 0.2 Because of the low conductivity element Si contained therein in an amount of up to 20 mol%, the conductivity of the negative electrode is low (only 0.2 mS/m), resulting in poor fast charge performance at 100mA/cm 2 The current density of (3) is only 5s, i.e. the cut-off voltage is reached, the charge capacity retention is only 5.6%, the coulomb efficiency is only 7.2%, which is far lower than in the examples.
The negative electrode of comparative example 4 was made of CuSnCrZnMgAlSiP alloy in which the contents of the respective components were 96.78wt% of Cu, 1.5wt% of Sn, 0.3wt% of Cr, 0.12wt% of Zn, 0.25wt% of Mg, 0.35wt% of Al, 0.55wt% of Si, 0.15wt% of P, and the concentration of the alloy was 100mA/cm 2 The charge capacity retention at the current density of (2) was only 13%, the coulombic efficiency was only 9.8%, which is far lower than in the examples, probably due to the too low content of the lithium philic component (Si+P content of only 0.7 wt%) therein, resulting in poor lithium philic effect.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and changes can be made by those skilled in the art without departing from the inventive concept and remain within the scope of the invention.
Claims (10)
1. The utility model provides a quick charge negative pole which characterized in that: the conductivity of the fast charge anode is not less than 10mS/m;
the component of the fast charge anode is Cu x M y A z Wherein M is three or more of Zn, ni, mn, sn, pb, mg, al, ga, ge, co, fe, V, cr, ti elements; a is one or more than one of B, si, P, se elements;
x, y, z satisfy the following relationship: x+y+z= 1,0.66, x is not less than 0.89,0.06 y is less than or equal to 0.24,0.04, z is less than or equal to 0.15, and z is less than or equal to y.
2. The fast charge anode of claim 1, wherein M comprises M1 and M2, wherein M1 is two or more of Zn, sn, pb, al, mg, ga, ge elements; m2 is one or more of Ni, mn, co, fe, V, cr, ti elements.
3. The fast charge anode of claim 1, wherein M is M1, wherein M1 is three or more of Zn, sn, pb, al, mg, ga, ge elements.
4. The fast charge anode of claim 1, wherein a is an element and z is 0.04.ltoreq.z.ltoreq.0.1.
5. The fast charge anode of claim 1, wherein a is two elements, and z is 0.06.ltoreq.z.ltoreq.0.12.
6. The fast charge anode according to claim 1, wherein a is three or more elements, and z is 0.07.ltoreq.z.ltoreq.0.15.
7. The fast charge anode of claim 1, wherein the thickness is 4 to 50um.
8. The method for preparing the fast-charging anode according to claim 1, comprising the steps of:
step 1: elemental powders of elements Cu, M and A are uniformly mixed according to the element proportion in the components, melted and cast into a block-shaped blank;
step 2: heating the block-shaped blank, hot rolling, cooling, and cold rolling to obtain a plate;
step 3: annealing the sheet material, and then performing secondary cold rolling to prepare a foil material;
step 4: and annealing the foil to remove stress to obtain the fast-charging anode.
9. The method for preparing a fast-charging anode according to claim 7, wherein the heat preservation is carried out for 2-8 hours at 900-1200 ℃ before the hot rolling in the step 2; the annealing of step 3 and step 4 is performed under a protective atmosphere.
10. Use of the fast charge anode of any one of claims 1 to 7 in an anodeless battery, which is an anodeless lithium battery or an anodeless sodium battery.
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