CN117461156A - Negative electrode for lithium ion secondary battery, method and device for manufacturing same, and lithium ion secondary battery - Google Patents
Negative electrode for lithium ion secondary battery, method and device for manufacturing same, and lithium ion secondary battery Download PDFInfo
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- CN117461156A CN117461156A CN202280041027.8A CN202280041027A CN117461156A CN 117461156 A CN117461156 A CN 117461156A CN 202280041027 A CN202280041027 A CN 202280041027A CN 117461156 A CN117461156 A CN 117461156A
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- Prior art keywords
- negative electrode
- current collector
- secondary battery
- ion secondary
- lithium ion
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 93
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims description 15
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 42
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 31
- 230000001376 precipitating effect Effects 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 53
- 239000001257 hydrogen Substances 0.000 claims description 43
- 229910052739 hydrogen Inorganic materials 0.000 claims description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 20
- 239000010949 copper Substances 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000003575 carbonaceous material Substances 0.000 claims description 7
- 210000001787 dendrite Anatomy 0.000 abstract description 11
- 239000011889 copper foil Substances 0.000 description 40
- 239000002245 particle Substances 0.000 description 19
- 239000007774 positive electrode material Substances 0.000 description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 238000010586 diagram Methods 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 238000005192 partition Methods 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000002482 conductive additive Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
Abstract
The invention provides a negative electrode of a lithium ion secondary battery, a manufacturing method and a manufacturing device thereof, and the lithium ion secondary battery, wherein dendrite growth of lithium metal is inhibited, and the negative electrode has enough weight energy density. The negative electrode NE of the lithium ion secondary battery LiB1 includes a negative electrode current collector N1 having a first surface N1a. The negative electrode current collector N1 has a plurality of protrusions PR1 on the first surface N1a. The protrusion PR1 has a surface capable of precipitating lithium. The projected area of the projection portion PR1 projected onto the first surface N1a was 10nm 2 ～10000nm 2 . Projection(s)The density of the raised portions PR1 was 1/μm 2 About 1000/μm 2 。
Description
Technical Field
The present invention relates to a negative electrode for a lithium ion secondary battery, a method for manufacturing the same, a device for manufacturing the same, and a lithium ion secondary battery.
Background
Examples of the chargeable and dischargeable power storage device include a secondary battery, an electric double layer capacitor, and the like. Examples of the power storage device using lithium ions include a lithium ion secondary battery, a lithium ion primary battery, and a lithium ion capacitor.
For example, patent document 1 discloses a lithium ion secondary battery having a positive electrode, a negative electrode, a separator, and a nonaqueous electrolyte. A technique of using lithium cobalt oxide or lithium nickel oxide as a positive electrode active material and carbon as a negative electrode active material is disclosed (the scope and examples of claims of patent document 1). As the carbon material, graphite (graphite) is often used. Graphite can intercalate or deintercalate 1 lithium ion per 6 carbon atoms of the six-membered ring. Patent documents 2 and 3 disclose a technique for suppressing dendrite growth of lithium metal by forming a fine-divided structure in a separator.
Prior art literature
Patent literature
Patent document 1: patent publication No. 2668678
Patent document 2: patent publication No. 5331627
Patent document 3: WO 2021/049609
Disclosure of Invention
In order to increase the gravimetric energy density of the lithium ion secondary battery, it is preferable that the negative electrode material of the lithium ion secondary battery is lightweight and is capable of inserting (or extracting) a large amount of lithium.
However, in the case of using a lithium ion secondary battery having graphite as a negative electrode material which is currently mainstream for an electric vehicle, the weight energy density is insufficient. On the other hand, in the case of using a lithium ion secondary battery having lithium metal as a negative electrode material for an electric vehicle, the weight energy density can be satisfied. However, in this case, there is a problem in that the positive electrode and the negative electrode are liable to be short-circuited due to dendrite growth of lithium metal.
The present invention has been made in view of the above problems, and an object of the present invention is to provide a negative electrode for a lithium ion secondary battery, a method and an apparatus for manufacturing the same, and a lithium ion secondary battery, wherein dendrite growth of lithium metal is suppressed and the negative electrode has a sufficient gravimetric energy density.
The negative electrode of the lithium ion secondary battery in the first aspect includes a current collector having a first surface. The current collector has a plurality of protrusions on the first surface. The protrusion has a surface capable of precipitating lithium.
The negative electrode of the lithium ion secondary battery has a protrusion. Lithium can be deposited on the surface of the protruding portion. Further, dendrite growth of lithium metal can be suppressed. Therefore, in the negative electrode of the lithium ion secondary battery, even if a large amount of lithium metal is precipitated, the problem of dendrite growth of lithium metal hardly occurs. That is, the negative electrode of the lithium ion secondary battery has both an effect of suppressing dendrite growth of lithium metal and a sufficient gravimetric energy density.
In the present specification, a negative electrode for a lithium ion secondary battery, which suppresses dendrite growth of lithium metal and has a sufficient gravimetric energy density, a method for manufacturing the same, a device for manufacturing the same, and a lithium ion secondary battery are provided.
Drawings
Fig. 1 is a schematic configuration diagram of a lithium ion secondary battery LiB1 according to the first embodiment.
Fig. 2 is a schematic diagram showing a cross section of the negative electrode NE of the lithium ion secondary battery LiB1 according to the first embodiment.
Fig. 3 is a schematic configuration diagram showing a configuration of a manufacturing apparatus for processing a negative electrode in the lithium ion secondary battery LiB1 according to the first embodiment.
Fig. 4 is a scanning electron micrograph showing the surface of the copper foil after irradiation of hydrogen radicals on the copper foil (first example).
Fig. 5 is a scanning electron micrograph showing the surface of the copper foil after irradiation of the copper foil with hydrogen radicals (second example).
Fig. 6 is a graph showing the measurement results of the irregularities on one line in fig. 5.
FIG. 7 shows the hydrogen supply amount and the area of the protrusion at 10nm 2 ～100nm 2 A graph of the relationship between the number of projections.
FIG. 8 shows the hydrogen supply amount and the area of the protrusion at 100m 2 ～1000nm 2 A graph of the relationship between the number of projections.
FIG. 9 shows that the hydrogen supply amount and the area of the protrusion are 1000nm 2 ～10000nm 2 A graph of the relationship between the number of projections.
Fig. 10 is a diagram showing a relationship between the amount of hydrogen supplied and the number of protrusions.
FIG. 11 shows the magnitude of the bias voltage and the area of the protrusion at 10nm 2 ～100nm 2 A graph of the relationship between the number of projections.
FIG. 12 shows the magnitude of the bias voltage and the area of the protrusion at 100nm 2 ～1000nm 2 A graph of the relationship between the number of projections.
FIG. 13 shows the magnitude of the bias voltage and the area of the protrusion at 1000nm 2 ～10000nm 2 A graph of the relationship between the number of projections.
Fig. 14 is a diagram showing a relationship between the magnitude of the bias voltage and the number of protrusions.
Fig. 15 is a photomicrograph showing the surface of the copper foil before hydrogen plasma irradiation.
Fig. 16 is a photomicrograph showing the surface of the copper foil after irradiation with hydrogen plasma.
Fig. 17 is a graph showing charge and discharge characteristics of a lithium ion secondary battery using a copper foil having a protrusion as a negative electrode.
Fig. 18 is a graph showing charge and discharge characteristics of a lithium ion secondary battery using a copper foil without a protrusion as a negative electrode.
Fig. 19 is a scanning microscope photograph (one of them) showing a cross section of a negative electrode of a lithium ion secondary battery having a protruding portion after repeated charge and discharge.
Fig. 20 is a scanning microscope photograph (second) showing a cross section of the negative electrode of the lithium ion secondary battery having the protruding portion after repeated charge and discharge.
Fig. 21 is a scanning microscope photograph showing a surface of lithium deposited on a negative electrode of a lithium ion secondary battery having a protrusion.
Fig. 22 is a photomicrograph showing the surface of the copper foil after oxygen plasma irradiation.
Fig. 23 is a graph showing charge and discharge characteristics of a lithium ion secondary battery when a copper foil having protrusions formed by oxygen plasma is used as a negative electrode.
Fig. 24 is a graph showing the results of component analysis of a copper foil having protrusions formed by oxygen plasma.
Detailed Description
Hereinafter, a negative electrode of a lithium ion secondary battery, a method and an apparatus for manufacturing the same, and a lithium ion secondary battery will be described with reference to the drawings.
(first embodiment)
1. Lithium ion secondary battery
Fig. 1 is a schematic configuration diagram of a lithium ion secondary battery LiB1 according to the first embodiment. The lithium ion secondary battery LiB1 has a positive electrode PE, a negative electrode NE, a separator Sp1, an electrolyte ES1, and a container V1.
The positive electrode PE is a positive electrode of the lithium ion secondary battery LiB1. The positive electrode PE has a positive electrode current collector P1 and a positive electrode active material layer P2. A positive electrode active material layer P2 is formed on the surfaces of the first surface P1a and the second surface P1b of the positive electrode collector P1.
The positive electrode current collector P1 is a metal substrate. The positive electrode current collector P1 is, for example, a metal foil. The shape of the positive electrode collector P1 may be other shapes. The material of the positive electrode current collector P1 is, for example, al or Ti. The material of the positive electrode current collector P1 may be a conductor of another metal or the like.
The positive electrode active material layer P2 contains a positive electrode active material, a conductive auxiliary agent, and a binder. The positive electrode active material layer P2 may further contain a thickener or the like. Examples of the positive electrode active material include lithium cobaltate, lithium manganate, lithium nickelate, and ternary systems. Examples of the conductive additive include carbon black. As the binder, SBR is exemplified. Examples of the thickener include carboxymethyl cellulose. Thus, the positive electrode active material layer P2 has lithium atoms.
The negative electrode NE is a negative electrode of the lithium ion secondary battery LiB1. The negative electrode NE has a negative electrode current collector N1. As described later, lithium is deposited on the negative electrode NE.
The negative electrode current collector N1 is a metal substrate. The negative electrode current collector N1 is, for example, a metal foil. The shape of the negative electrode current collector N1 may be other shapes. The negative electrode current collector N1 is made of Cu, for example. The negative electrode current collector N1 is, for example, a copper plate or a copper foil. The negative electrode current collector N1 may be made of another metal or other conductive material.
The separator Sp1 serves to electrically insulate the positive electrode PE from the negative electrode NE. The separator Sp1 is permeable to lithium ions in the electrolyte ES 1.
The electrolyte ES1 has a characteristic of transferring lithium ions between the positive electrode PE and the negative electrode NE. Electrolyte ES1 fills vessel V1. The electrolyte ES1 is a liquid obtained by dissolving a lithium salt such as lithium hexafluorophosphate (LiPF 6) in dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), or the like.
The container V1 accommodates the positive electrode PE, the negative electrode NE, the separator Sp1, and the electrolyte ES1 therein. The container V1 is made of a material that is not easily reacted with the electrolyte ES 1.
2. Protruding part
Fig. 2 is a schematic diagram showing a cross section of the negative electrode NE of the lithium ion secondary battery LiB1 according to the first embodiment. The negative electrode current collector N1 has a first surface N1a. The first surface N1a is the other surface of the negative electrode current collector N1. A plurality of protrusions PR1 are formed on the first surface N1a of the negative electrode current collector N1. The protrusion PR1 has a surface capable of precipitating lithium.
The protrusion PR1 is a portion of the negative electrode current collector N1 that partially protrudes from the first surface N1a. The protrusion PR1 may be composed of a single particle GR1 or may be composed of a plurality of particles GR 1. In this case, the material of the particles GR1 is preferably the same as that of the negative electrode current collector N1. The particles GR1 are preferably fused with the first surface N1a of the negative electrode current collector N1 and integrated with the negative electrode current collector N1. This is because the adhesion between the negative electrode current collector N1 and the particles GR1 is improved, and therefore the particles GR1 are prevented from being peeled off from the negative electrode current collector N1.
The size of the plane of the protrusion PR1 is observed from a direction perpendicular to the first face N1a of the negative electrode current collector N1 using a scanning electron microscope. The projected area of the projection portion PR1 projected onto the first surface N1a was 10nm 2 ～10000nm 2 . Preferably 20nm 2 ～5000nm 2 . The average value of the maximum length of the projection region obtained by projecting the projection PR1 onto the first surface N1a is, for example, 10nm to 200nm. Here, the maximum length of the projection region means a length at which a line segment passing through the inside of the projection region becomes maximum.
For example, every 10 μm of the first face N1a of the negative electrode current collector N1 2 There are 10 to 10000 protrusions PR1. That is, the density of the protrusions in the projection area obtained by projecting the protrusions PR1 onto the first surface N1a is 1/μm 2 About 1000/μm 2 . Preferably 2/μm 2 About 800 pieces/mu m 2 . More preferably 3/μm 2 About 500/μm 2 . The projection area of the projection portion PR1 onto the first surface N1a is, for example, 1/10 to 8/10 of the area of the first surface.
As described later, when the protrusion PR1 is formed by irradiation with hydrogen plasma, it is considered that the protrusion PR1 is formed as follows. The copper particles GR1 are knocked out from the first surface N1a of the negative electrode collector N1, and the knocked-out particles GR1 are reattached to the first surface N1a of the negative electrode collector N1 and fused to the first surface N1a of the negative electrode collector N1, thereby forming the protrusion PR1. The size and density of the protrusion PR1 are considered to be important factors for precipitation of lithium.
The protrusion PR1 functions as a starting point of precipitation of lithium. In addition, it is also considered that by suppressing movement of lithium ions in a direction parallel to the first surface N1a of the negative electrode current collector N1, it is possible to align the deposition direction of lithium metal and suppress dendrite growth of lithium metal.
3. Lithium ion mediated charge-discharge reaction
3-1. Charge-discharge reaction
The charge-discharge reaction is a chemical reaction represented by the following chemical reaction formula, for example.
Formula (1) is a reaction in the anode NE. Equation (2) is a reaction in the positive electrode active material layer P2. Both reactions have lithium ion and electron interactions. The charge-discharge reaction is a chemical reaction in which lithium ions intervene in the positive electrode PE or the negative electrode NE to generate transfer of electrons. By this charge-discharge reaction, phenomena such as intercalation and deintercalation of lithium ions, precipitation, deposition, adsorption, and dissolution of lithium or lithium compounds can be generated. In the case of precipitation of lithium or a lithium compound, for example, a charge-discharge reaction may occur outside the positive electrode active material layer P2 or the negative electrode NE. The types of charge and discharge reactions vary depending on the materials of the positive electrode active material layer P2 and the negative electrode NE.
4. Manufacturing apparatus
A manufacturing apparatus for forming the protrusion PR1 on the first surface N1a of the negative electrode current collector N1 will be described.
Fig. 3 is a schematic configuration diagram showing a configuration of a manufacturing apparatus for processing a negative electrode in the lithium ion secondary battery LiB1 according to the first embodiment. The manufacturing apparatus 1 has a plasma generation chamber 46 and a reaction chamber 10. The plasma generation chamber 46 is for generating plasma therein and also generating radicals supplied to the reaction chamber 10. The reaction chamber 10 forms a protrusion PR1 on the negative electrode current collector N1 by radicals generated in the plasma generation chamber 46.
The manufacturing apparatus 1 further includes a waveguide 47, a quartz window 48, and a slot antenna 49. The waveguide 47 is used to introduce the microwave 39. The slit antenna 49 is used to introduce the microwave 39 from the quartz window 48 to the plasma generation chamber 46.
The plasma generation chamber 46 is used to generate Surface Wave Plasma (SWP) by microwaves 39. The plasma generation chamber 46 is provided with a radical source introduction port 42. The radical source introduction port 42 is for supplying a gas as a radical source into the plasma 61 generated in the plasma generation chamber 46.
A partition 44 is provided between the plasma generation chamber 46 and the reaction chamber 10. The partition wall 44 serves to partition the plasma generation chamber 46 from the reaction chamber 10. The partition wall 44 also doubles as the first electrode 22 to which the voltage is applied. The partition 44 is formed with a through hole 14. For supplying radicals generated in the plasma generation chamber 46 to the reaction chamber 10.
The reaction chamber 10 is used to generate a Capacitively Coupled Plasma (CCP). In addition, the reaction chamber 10 is also used to form a protrusion PR1 on the negative electrode current collector N1. The reaction chamber 10 has a second electrode 24, a heater 25, a raw material inlet 12, and an exhaust port 16. The second electrode 24 is used to apply a voltage between it and the first electrode 22. The heater 25 is used to heat the negative electrode current collector N1 and control the temperature of the negative electrode current collector N1. In the first embodiment, the material inlet 12 is not supplied with any material, and may be omitted. The exhaust port 16 is connected to a vacuum pump or the like. The vacuum pump is used to adjust the pressure inside the reaction chamber 10.
As described above, the partition wall 44 doubles as the first electrode 22 to which a voltage is applied between the partition wall and the second electrode 24. A power supply and a circuit are connected to the first electrode 22. For controlling the potential of the first electrode 22 in time. The second electrode 24 is used to apply a voltage between it and the first electrode 22. The second electrode 24 is also a mounting table for mounting the negative electrode current collector N1. The second electrode 24 is grounded.
The distance between the first electrode 22 and the second electrode 24 is about 5cm. Of course, this value is not limiting.
5. Method for manufacturing negative electrode
5-1. Protrusion forming step
First, the negative electrode current collector N1 before the protrusion PR1 is formed is placed in the manufacturing apparatus 1. At this time, the first face N1a of the negative electrode collector N1 faces upward, and the second face N1b is in contact with the second electrode 24. Then, the microwaves 39 are introduced into the waveguide 47. The microwaves 39 are introduced into the plasma generation chamber 46 from the quartz window 48 through the slot antenna 49. Thereby, the high-density plasma 60 is generated.
The high-density plasma 60 diffuses into the plasma generation chamber 46 to become plasma 61. The plasma 61 contains ions of a radical source supplied from the radical source introduction port 42. As the radical source, a gas containing hydrogen is used. Most of the ions in the plasma 61 collide with the partition wall 44. The radicals 38 enter the reaction chamber 10 through the through holes 14 of the partition wall 44. Then, a voltage is applied between the first electrode 22 and the second electrode 24. Thereby, the plasma 34 is generated inside the reaction chamber 10.
Radicals 38 are present in the atmosphere of plasma 34. In the atmosphere of the plasma 34, the protrusion PR1 grows on the first surface N1a of the negative electrode current collector N1. At this time, the copper particles GR1 are scattered from the first surface N1a of the negative electrode current collector N1, and are attached again to the first surface N1a of the negative electrode current collector N1.
The pressure in the reaction chamber 10 is in the range of 5 to 2000mTorr (0.65 Pa to 267 Pa). The temperature of the negative electrode current collector N1 is in the range of 0 to 500 ℃. Preferably from 0℃to 400 ℃. These are, of course, examples and are not limited to these numerical ranges.
6. Method for manufacturing lithium ion secondary battery
6-1. Negative electrode manufacturing process
As described above, the negative electrode NE was produced. That is, a gas containing hydrogen is plasmatized and supplied to the current collector, and a plurality of protrusions made of the same material as the current collector are formed on the first surface of the current collector.
6-2. Positive electrode manufacturing process
The positive electrode PE was produced. For this purpose, a positive electrode active material layer P2 is formed on the positive electrode current collector P1. For this purpose, for example, a slurry containing a positive electrode active material is produced, applied to the positive electrode current collector P1, and dried.
6-3. Electrode body manufacturing process
The positive electrode PE and the negative electrode NE are wound with the separator Sp1 therebetween to produce an electrode body.
6-4. Sealing process
The electrode body is inserted into the case, and the case is filled with an electrolyte. The housing is then sealed.
6-5. Others
Other steps such as an aging step may be performed.
7. Effects of the first embodiment
The negative electrode NE of the lithium ion secondary battery LiB1 of the first embodiment has a protrusion PR1. The protrusion PR1 is obtained by fusing a single particle GR1 or an aggregate of a plurality of particles GR1 to the first surface N1a of the negative electrode current collector N1. Therefore, lithium is likely to be deposited from the protrusion PR1. Therefore, the anode NE does not contain an anode active material for lithium intercalation, which is a carbonaceous material.
8. Modification examples
8-1. Protrusion forming step
As the protrusion forming step, other processes may be performed. Examples of the treatment in the protrusion forming step include a press-like pressure treatment, a chemical treatment, and sputtering using a metal target such as copper or aluminum.
8-2. Plasma gas
The plasma gas of the first embodiment is hydrogen. However, other gases may be used as the plasma gas. For example, oxygen may be used.
8-3. Plasma device
A plasma device other than the first embodiment may be used. Such as Inductively Coupled Plasma (ICP). Of course, other plasma devices may be used.
Examples
(experiment 1)
1. Protruding part
1-1. Capacitively Coupled Plasma (CCP)
Inside the manufacturing apparatus 1, a protrusion PR1 is formed on a copper foil (copper substrate). The conditions at this time are shown in Table 1. The flow rate of hydrogen was 50sccm. The flow rate of Ar was 5sccm. The power (MW power) of the microwaves is 400W. The power applied between the electrodes (CCP power) was 400W. The temperature of the heater 25 was 560 ℃. The treatment time was 10 minutes.
The gas is not supplied from the raw material inlet 12 into the manufacturing apparatus 1. Thus, a plasma of hydrogen gas is generated, and hydrogen radicals are supplied to the copper foil.
TABLE 1
Fig. 4 is a scanning electron micrograph (1) showing the surface of the copper foil after irradiation of hydrogen radicals on the copper foil. Fig. 4 shows a pattern in which a large number of copper particles are deposited on the surface of a copper foil to form protrusions. Based on the shape of the particles observed, it is considered that the copper particles that have been knocked out of the copper foil by irradiation with hydrogen radicals reattach to the surface of the copper foil. Thus, the maximum length of the projected area in which 1 copper particle (Cu grain) is projected on the copper foil is about 40nm. The maximum length of the projection region obtained by projecting the protrusion PR1 composed of the aggregate of copper particles onto the copper foil is 100nm to 200nm. The projection region occupies 1/10 or more of the area of the first surface N1a of the negative electrode collector N1.
1-2 Inductively Coupled Plasma (ICP)
In this experiment, the protrusion forming step was performed using an ICP apparatus instead of the manufacturing apparatus 1. Table 2 shows the processing conditions in the ICP apparatus.
TABLE 2
1-2-1. Hydrogen supply amount and protruding part
The number and size of the protrusions were examined by changing the amount of hydrogen supplied. The bias applied to the substrate support portion was 0V.
Fig. 5 is a scanning electron micrograph (photograph 2) showing the surface of the copper foil after irradiation of hydrogen radicals on the copper foil. The white region is a region of the protrusion.
Fig. 6 is a graph showing the measurement results of the irregularities on one line in fig. 5. The horizontal axis of fig. 6 is position. The vertical axis of fig. 6 is the height from the reference plane. As shown in FIG. 6, the projections were observed to have a height of about 200nm and a width of about 200nm. As estimated from fig. 4, the height and width of the protruding portion are the same.
The area of the white region in the scanning electron microscope was measured using the function of the scanning electron microscope. The area of the white region corresponds to the two-dimensional size of the protrusion.
FIG. 7 shows the hydrogen supply amount and the area of the protrusion at 10nm 2 ～100nm 2 A graph of the relationship between the number of projections. The horizontal axis of fig. 7 indicates the hydrogen supply amount (sccm). The vertical axis of FIG. 7 is every 10 μm 2 The number of the protruding portions. When the hydrogen supply amount was 100sccm, the area was 10nm 2 ～100nm 2 The number of small protrusions of (a) tends to increase.
FIG. 8 shows the hydrogen supply amount and the area of the protrusion at 100nm 2 ～1000nm 2 A graph of the relationship between the number of projections. The horizontal axis of fig. 8 indicates the hydrogen supply amount (sccm). The vertical axis of FIG. 8 is every 10 μm 2 The number of the protruding portions. When the hydrogen supply amount was 50sccm, the area was 100nm 2 ～1000nm 2 The number of the intermediate protrusions tends to increase.
FIG. 9 shows that the hydrogen supply amount and the area of the protrusion are 1000nm 2 ～10000nm 2 A graph of the relationship between the number of projections. The horizontal axis of fig. 9 indicates the hydrogen supply amount (sccm). The vertical axis of FIG. 9 is every 10 μm 2 The number of the protruding portions. When the hydrogen supply amount was 100sccm, the area was 1000nm 2 ～10000nm 2 The number of large protrusions of (a) tends to increase.
Fig. 10 is a diagram showing a relationship between the amount of hydrogen supplied and the number of protrusions. The horizontal axis of fig. 10 indicates the hydrogen supply amount (sccm). The vertical axis of FIG. 10 is every 10 μm 2 The number of the protruding portions. When the amount of hydrogen supplied is 100sccm, the number of projections tends to increase.
In this way, when the amount of hydrogen supplied is 100sccm, the number of projections tends to increase. In this case, the number of small protrusions and large protrusions is large.
When the hydrogen supply amount was 50sccm, the area was 100nm 2 ～1000nm 2 The number of the intermediate protrusions tends to increase. In this case, the number of large protrusions and small protrusions is not large. Therefore, in this case, the size of the protruding portion is uniform to a moderate extent.
1-2-2. Bias and protrusion
The supply amount of hydrogen was set to 100sccm, and the bias applied to the second electrode 24 was changed. The bias applied to the second electrode 24 is a DC bias.
FIG. 11 shows the magnitude of the bias voltage and the area of the protrusion at 10nm 2 ～100nm 2 A graph of the relationship between the number of projections. The horizontal axis of fig. 11 is the bias voltage. The vertical axis of FIG. 11 is every 10 μm 2 The number of the protruding portions. As shown in FIG. 11, the area of the protrusion is 10nm by applying a negative bias 2 ～100nm 2 The number of the protrusions is reduced.
FIG. 12 shows the magnitude of the bias voltage and the area of the protrusion at 100nm 2 ～1000nm 2 A graph of the relationship between the number of projections. The horizontal axis of fig. 12 is bias. The vertical axis of FIG. 12 is every 10 μm 2 The number of the protruding portions. As shown in FIG. 12, when a bias of-25V is applied, the area of the protrusion is 100nm 2 ～1000nm 2 The number of the protrusions is the largest. Thus, the formation area is 100nm 2 ～1000nm 2 In the case of a substrate having a large number of protrusions, a bias of about-25V is preferably applied.
FIG. 13 shows the magnitude of the bias voltage and the area of the protrusion at 1000nm 2 ～10000nm 2 A graph of the relationship between the number of projections. The horizontal axis of fig. 13 is the bias voltage. The vertical axis of FIG. 13 is every 10. Mu.m 2 The number of the protruding portions. As shown in FIG. 13, when a bias of-50V is applied, the area of the protrusion is 1000nm 2 ～10000nm 2 The number of the protrusions is the largest. Thus, in the formation of 1000nm 2 ～10000nm 2 In the case of a substrate having a large number of protrusions, a bias of about-50V is preferably applied.
Fig. 14 is a diagram showing a relationship between the magnitude of the bias voltage and the number of protrusions. The horizontal axis of fig. 14 is the bias voltage. The vertical axis of FIG. 14 is every 10. Mu.m 2 The number of the protruding portions. In the case of applying a negative bias, the larger the absolute value of the bias, the number of protrusions tends to decrease.
With a bias of 0V, the area is 10nm 2 ～100nm 2 The number of small protrusions of (a) tends to increase. With a bias of-25V, the area is 100nm 2 ～1000nm 2 The number of the intermediate protrusions tends to increase. At a bias of-50V, the area is 1000nm 2 ～10000nm 2 The number of large protrusions of (a) tends to increase. In the case of the bias of-100V, the protrusion tends to be difficult to form regardless of the size of the protrusion.
The larger the absolute value of the negative bias, the more likely the hydrogen particles collide with the substrate. In addition, the kinetic energy of the hydrogen particles is also high.
By selecting the supply amount of hydrogen and the value of the bias voltage in this way, the size and the number of the protrusions formed on the substrate can be controlled to a certain extent.
(experiment 2)
2. Lithium ion secondary battery
2-1. Protruding part
Inside the manufacturing apparatus 1, a protrusion PR1 is formed on a copper foil (copper substrate). The conditions at this time are shown in Table 3. The flow rate of the hydrogen gas was 100sccm. The flow rate of Ar was 5sccm. The power (MW power) of the microwaves is 400W. The power applied between the electrodes (CCP power) was 400W. The temperature of the copper foil was 700 ℃. The treatment time was 10 minutes.
The raw material gas is not supplied into the manufacturing apparatus 1. Thus, a plasma of hydrogen gas is generated, and hydrogen radicals are supplied to the copper foil.
TABLE 3
Fig. 15 is a photomicrograph showing the surface of the copper foil before hydrogen plasma irradiation.
Fig. 16 is a photomicrograph showing the surface of the copper foil after irradiation with hydrogen plasma. As shown in fig. 16, a plurality of protrusions are formed on the surface of the copper foil.
2-2 charge-discharge characteristics of lithium ion secondary battery
The lithium ion secondary battery LiB1 of the first embodiment was manufactured. The positive electrode current collector P1 is aluminum, and the positive electrode active material is lithium cobaltate. The negative electrode current collector N1 is copper. The cathode is copper foil only and does not contain carbon materials. The electrolyte was LiPF6 at 1M. The positive electrode active material layer was a region having a diameter of 1.6 cm. The anode active material layer was a region having a diameter of 1.3 cm.
The positive electrode active material layer contains lithium cobaltate, a conductive auxiliary agent, and a binder. The conductive additive is acetylene black. The binder is PVDF. The weight ratio of lithium cobaltate, acetylene black and PVDF is 100:5:3.
fig. 17 is a graph showing charge and discharge characteristics of a lithium ion secondary battery using a copper foil having a protrusion as a negative electrode. The horizontal axis of fig. 17 shows capacitance. The vertical axis of fig. 17 is voltage. The charge current or the discharge current was 0.5mA. The capacity of the lithium ion secondary battery was 12.6mAh.
Fig. 18 is a graph showing charge and discharge characteristics of a lithium ion secondary battery using a copper foil without a protrusion as a negative electrode. The horizontal axis of fig. 17 shows capacitance. The vertical axis of fig. 17 is voltage. The charge current or the discharge current was 0.5mA. The capacity of the lithium ion secondary battery is about 0.6 mAh.
In this way, the copper foil without carbonaceous material, on which the protrusions are formed, functions as a negative electrode of the lithium ion secondary battery. In addition, in the case where the protrusion is not present, the copper foil does not function as a negative electrode of the lithium ion secondary battery.
2-3. Microscopic photograph
Fig. 19 shows a scanning microscope photograph (photograph 1) of a cross section of a negative electrode of a lithium ion secondary battery having a protruding portion after repeated charge and discharge. As shown in fig. 19, lithium is deposited on the copper foil. In addition, the surface of lithium was flat and no dendrite growth was observed. Since lithium is deposited in this manner, the negative electrode does not need a lithium intercalation material such as a carbon material.
Fig. 20 shows a scanning microscope photograph (photograph 2) of a cross section of a negative electrode of a lithium ion secondary battery having a protruding portion after repeated charge and discharge. As shown in FIG. 20, lithium has a film thickness of about 40. Mu.m. In addition, as shown in fig. 20, the surface of the precipitated lithium was very flat and dendrites were not generated.
Fig. 21 is a scanning microscope photograph showing a surface of lithium deposited on a negative electrode of a lithium ion secondary battery having a protrusion.
In the case where the copper foil has the protrusions, the protrusions have a surface capable of precipitating lithium.
(experiment 3)
3. Oxygen plasma
3-1. Protruding part
Oxygen is used instead of hydrogen. The plasma conditions are shown in table 4.
TABLE 4
Fig. 22 is a photomicrograph showing the surface of the copper foil after oxygen plasma irradiation. As shown in the figure 22 of the drawings,
3-2. charge-discharge characteristics of lithium ion secondary battery
A lithium ion secondary battery was fabricated in the same manner as in experiment 2.
Fig. 23 shows charge and discharge characteristics of a lithium ion secondary battery in which a copper foil having protrusions formed by oxygen plasma is used as a negative electrode. The horizontal axis of fig. 23 shows capacitance. The vertical axis of fig. 23 is voltage. The charge current or the discharge current was 0.5mA. The capacity of the lithium ion secondary battery was 10.58mAh.
Fig. 24 is a graph showing the results of component analysis of a copper foil having protrusions formed by oxygen plasma. As shown in fig. 24, the copper foil after the treatment with oxygen plasma contains oxygen atoms to some extent.
(additionally remembered)
The negative electrode of the lithium ion secondary battery in the first aspect includes a current collector having a first surface. The current collector has a plurality of protrusions on the first surface. The protrusion has a surface capable of precipitating lithium.
In the negative electrode of the lithium-ion secondary battery according to the second aspect, the projected area obtained by projecting the projection onto the first surface is 10nm 2 ～10000nm 2 . The density of the protrusions was 1/μm 2 About 1000/μm 2 。
In the negative electrode of the lithium ion secondary battery according to the third aspect, the average value of the maximum lengths of the projection regions obtained by projecting the protrusions onto the first surface is 10nm to 200nm. The area occupied by the projection area is more than 1/10 of the first surface.
In the negative electrode of the lithium ion secondary battery according to the fourth aspect, the protrusion is made of the same material as the current collector, and is integrated with the current collector by being fused with the first surface of the current collector.
In the negative electrode of the lithium ion secondary battery according to the fifth aspect, the current collector is made of copper.
The negative electrode of the lithium ion secondary battery in the sixth aspect is free of carbonaceous material.
The lithium ion secondary battery in the seventh aspect has a positive electrode and a negative electrode. The negative electrode includes a current collector having a first surface. The current collector has a plurality of protrusions on the first surface. The protrusion has a surface capable of precipitating lithium.
In the method for manufacturing the negative electrode of the lithium-ion secondary battery according to the eighth aspect, the hydrogen-containing gas is plasmatized and supplied to the current collector, and a plurality of protrusions made of the same material as the current collector are formed on the first surface of the current collector.
In the method for manufacturing the negative electrode of the lithium ion secondary battery according to the ninth aspect, the protrusion and the current collector are made of the same material, and are fused to the first surface of the current collector.
The apparatus for manufacturing a negative electrode of a lithium ion secondary battery according to the tenth aspect comprises: a plasma generation chamber for plasmatizing a gas containing hydrogen gas; a reaction chamber for supplying the gas converted into plasma in the plasma generation chamber to the current collector, and forming a plurality of protrusions made of the same material as the current collector on the first surface of the current collector.
In the apparatus for manufacturing a negative electrode of a lithium ion secondary battery according to the eleventh aspect, the reaction chamber is formed with a protrusion that is made of the same material as the current collector, and that is integrated with the current collector by being integrated with the first surface of the current collector.
Symbol description
LiB1 … lithium ion secondary battery
PE … anode
P1 … positive electrode current collector
P2 … Positive electrode active Material layer
NE … negative electrode
N1 … negative electrode current collector
N1a … first side
PR1 … protrusion
GR1 … particles
Sp1 … spacer
ES1 … electrolyte
V1 … container
Claims (11)
1. A negative electrode for a lithium ion secondary battery is provided with a current collector having a first surface,
the current collector has a plurality of protrusions on the first face,
the protrusion has a surface capable of precipitating lithium.
2. The negative electrode of a lithium ion secondary battery according to claim 1, wherein,
the projected area of the projection area obtained by projecting the projection onto the first surface is 10nm 2 ～10000nm 2 ，
The density of the protruding parts is 1/μm 2 About 1000/μm 2 。
3. The negative electrode of a lithium ion secondary battery according to claim 1 or 2, wherein,
the average value of the maximum length of the projection area obtained by projecting the projection onto the first surface is 10nm to 200nm,
the area occupied by the projection area is more than 1/10 of the first surface.
4. The negative electrode of a lithium ion secondary battery according to any one of claims 1 to 3, wherein the protrusion is made of the same material as the current collector, and is integrated with the current collector by being fused with the first surface of the current collector.
5. The negative electrode of a lithium ion secondary battery according to any one of claims 1 to 4, wherein a material of the current collector is copper.
6. The negative electrode of a lithium ion secondary battery according to any one of claims 1 to 5, which has no carbon material.
7. A lithium ion secondary battery has a positive electrode and a negative electrode,
the negative electrode includes a current collector having a first surface,
the current collector has a plurality of protrusions on the first face,
the protrusion has a surface capable of precipitating lithium.
8. A method of manufacturing a negative electrode of a lithium ion secondary battery, comprising:
a gas containing hydrogen is plasmatized and supplied to a current collector,
a plurality of protrusions made of the same material as the current collector are formed on the first surface of the current collector.
9. The method for manufacturing a negative electrode of a lithium ion secondary battery according to claim 8, wherein the protrusion is made of the same material as the current collector and is fused to the first surface of the current collector.
10. An apparatus for manufacturing a negative electrode of a lithium ion secondary battery, comprising:
a plasma generation chamber for plasmatizing a gas containing hydrogen gas; and
a reaction chamber for supplying the gas converted into plasma in the plasma generating chamber to the current collector, and forming a plurality of protrusions made of the same material as the current collector on the first surface of the current collector.
11. The apparatus for manufacturing a negative electrode of a lithium ion secondary battery according to claim 10, wherein a protrusion is formed in the reaction chamber, the protrusion being made of the same material as the current collector, and being integrated with the current collector by being integrated with the first surface of the current collector.
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| PCT/JP2022/021389 WO2022259871A1 (en) | 2021-06-08 | 2022-05-25 | Negative electrode for lithium-ion secondary battery, manufacturing method and manufacturing device therefor, and lithium-ion secondary battery |
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| JP7117658B2 (en) * | 2017-05-29 | 2022-08-15 | パナソニックＩｐマネジメント株式会社 | Lithium metal secondary battery |
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| KR102187992B1 (en) * | 2018-12-18 | 2020-12-08 | 한양대학교 산학협력단 | Anode for lithium secondary battery comprising lithiophilic coating layer, method for producing the same, and lithium secondary battery comprising the same |
| CN111403687A (en) * | 2020-03-27 | 2020-07-10 | 清华大学深圳国际研究生院 | Lithium metal cathode, preparation method and lithium ion battery |
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