CN106374083B - Silicon substrate negative electrode and preparation method thereof and lithium ion battery - Google Patents
Silicon substrate negative electrode and preparation method thereof and lithium ion battery Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 144
- 239000010703 silicon Substances 0.000 title claims abstract description 144
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000000758 substrate Substances 0.000 title abstract 6
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000002002 slurry Substances 0.000 claims description 89
- 239000011230 binding agent Substances 0.000 claims description 58
- 239000007773 negative electrode material Substances 0.000 claims description 41
- 238000000576 coating method Methods 0.000 claims description 26
- 239000006258 conductive agent Substances 0.000 claims description 26
- 239000011248 coating agent Substances 0.000 claims description 20
- 239000002041 carbon nanotube Substances 0.000 claims description 13
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 239000011267 electrode slurry Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical group [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 239000003273 ketjen black Substances 0.000 claims description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 4
- 239000000126 substance Substances 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 153
- 229920003048 styrene butadiene rubber Polymers 0.000 description 43
- 239000002174 Styrene-butadiene Substances 0.000 description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 239000002131 composite material Substances 0.000 description 11
- 229910021383 artificial graphite Inorganic materials 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 238000007599 discharging Methods 0.000 description 9
- 229910052814 silicon oxide Inorganic materials 0.000 description 9
- 229920005822 acrylic binder Polymers 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000000080 wetting agent Substances 0.000 description 7
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000005543 nano-size silicon particle Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000010586 diagram 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
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000002409 silicon-based active material Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001291 vacuum drying 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a kind of silicon substrate negative electrode and preparation method thereof and lithium ion batteries.Silicon substrate negative electrode of the present invention includes that the collector has two surfaces being oppositely arranged, and is coated with the first active layer on a surface, the second active layer is coated on another surface.Silicon substrate negative electrode structure stability of the present invention is stablized, and chemical property is good, and preparation method process conditions are controllable, and the silicon substrate negative electrode performance of preparation is stablized.It is high that lithium ion battery of the present invention contains silicon substrate negative electrode, stable cycle performance, long service life, and security performance.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a high-gram-capacity silicon-based negative electrode, a preparation method thereof and a lithium ion battery.
Background
Lithium ion batteries are widely used in mobile phones and notebook batteries, power batteries, energy storage batteries, and the like due to their excellent properties such as high voltage, high energy density, and long cycle life. The battery of the mobile phone and the notebook computer is completely occupied by the lithium ion battery, and the battery of other types can not meet the strict requirements of the portable intelligent equipment. With the development of lithium ion battery technology, the proportion of the lithium ion battery in the power battery energy storage battery is also getting larger and larger, and from the current development trend, the lithium ion battery is in a rapid development stage and has a wide application prospect.
With the increase of the light weight, the multi-functionality and the screen of smart phones and notebook computers, the existing lithium ion batteries are also difficult to meet the increasingly harsh requirements of consumer electronics on the batteries, and a novel technology is urgently needed to effectively improve the specific energy of the lithium ion batteries. Lithium ion batteries generally include four key materials, including a negative electrode, a separator, an electrolyte, a positive electrode, and other auxiliary materials. In the four key materials, the negative electrode and the positive electrode are core materials, and the gram capacity and the lithium intercalation and deintercalation voltage of the negative electrode and the positive electrode determine the specific energy of the lithium ion battery. The commonly used anode materials of the current lithium ion battery comprise lithium cobaltate, lithium manganate, ternary lithium iron phosphate and lithium iron phosphate, and the gram capacity is between 100 and 200 mAh/g; the commonly used cathode material is a carbon cathode material, and the gram capacity is 250-360 mAh/g.
The gram capacity of the negative electrode material is one of effective ways for improving the specific energy of the battery. At present, graphite, silicon-based, tin-based, nano carbon materials, metal oxides and the like are used as negative electrode materials of lithium ion batteries. However, the silicon-based negative electrode material is accompanied with severe volume expansion in the lithium intercalation and deintercalation process, leading to pulverization and exfoliation of electroactive substances and continuous formation of a solid electrolyte membrane, directly leading to the problems of rapid gram capacity attenuation, low charging and discharging efficiency, short cycle life and the like, and leading to severe limitation on the application of the silicon-based negative electrode material with high gram capacity in the lithium ion battery. Although the volume expansion defect of silicon in the process of lithium intercalation and deintercalation is overcome by adopting a silicon-based negative electrode material, such as a carbon-coated silicon composite negative electrode material, the effect is limited, and the composite material still undergoes volume expansion in the process of charging and discharging, so that the problems of pulverization and shedding of a silicon-carbon composite active substance and the formation of a solid electrolyte membrane still occur, and the problems of fast capacity attenuation, short cycle life and the like are still directly caused. Although the adhesive is added into the silicon-based composite negative electrode, the adhesive strength of the conventional adhesive system is limited, and the negative active materials are peeled off in the circulation process of the silicon-based negative electrode material, so that effective electric contact is lost, and the defects of serious volume expansion, quick capacity attenuation, short cycle life and the like exist in the charge and discharge process of the battery, so that the application of the silicon-based negative electrode material with high gram capacity to the lithium ion battery is severely limited.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a silicon-based negative electrode and a preparation method thereof, so as to solve the technical problems of unstable structure and poor electrochemistry of a silicon-based electrode plate caused by volume expansion of a silicon-based active material in the charging and discharging processes of the conventional battery.
The invention also aims to provide a silicon-based negative electrode lithium ion battery to solve the technical problems of fast capacity attenuation, poor cyclicity and short service life of the conventional silicon-based negative electrode lithium ion battery.
In order to achieve the above object, according to one aspect of the present invention, a silicon-based negative electrode is provided. The silicon-based negative electrode comprises a current collector, wherein the current collector comprises two oppositely arranged surfaces, a first active layer is coated on one surface, and a second active layer is coated on the other surface; wherein,
the first active layer comprises the following components in parts by weight:
94.5 to 96.0 portions of silicon-based negative electrode material
1.0-1.5 parts of first conductive agent
2.5-3.0 parts of modified SBR binder
The second active layer comprises the following components in parts by weight:
in another aspect of the invention, a method for preparing a silicon-based negative electrode is provided. The preparation method of the silicon-based negative electrode comprises the following steps:
preparing a first active layer slurry according to the following components contained in the first active layer slurry and the component proportion thereof and a preparation method of the electrode slurry, wherein the first active layer slurry comprises the following components in parts by weight:
preparing a second active layer slurry according to the components contained in the second active layer slurry and the component proportion thereof and the preparation method of the electrode slurry, wherein the second active layer slurry comprises the following components in parts by weight:
coating the first active layer slurry on one surface of two oppositely arranged surface negative current collectors, and drying to form a first active layer;
and coating the second active layer slurry on the other surface of the negative current collector, and drying to form a second active layer.
In yet another aspect of the present invention, a lithium ion battery is provided, which contains the silicon-based negative electrode of the present invention or a silicon-based negative electrode prepared by the preparation method of the present invention.
Compared with the prior art, the silicon-based negative electrode has the advantages that the modified SBR binder contained in the first active layer can enhance the bonding performance between the silicon-based negative electrode materials and between the first active layer of the silicon-based negative electrode materials and the negative current collector, the bonding strength between the first active layer and the negative current collector is improved, the uniformity of the first active layer is improved due to the existence of the modified SBR binder, and the liquid retention performance of the first active layer on electrolyte is improved. The second active layer is compounded by adopting a conventional non-modified SBR binder and a modified acrylic acid binder, so that the composite binder not only improves the structural stability of the second active layer, but also can form a more stable SEI film in the first charging process. Therefore, the first active layer and the second active layer play a role in electrochemical synergy, and can effectively inhibit full charge rebound of the silicon-based negative electrode and improve the cycle performance of the silicon-based negative electrode on the basis of remarkably improving the structural stability and high gram capacity of the silicon-based negative electrode.
According to the preparation method of the silicon-based negative electrode, the surface of one side of a negative current collector is coated with the modified SBR binder which is used as the binder of the silicon-based negative electrode material to prepare the water-based slurry, the other side of the current collector is coated with the conventional non-modified SBR binder and the modified acrylic acid binder which are compounded with the binder of the silicon-based negative electrode material to prepare the water-based slurry, the prepared silicon-based negative electrode has excellent structural stability through the synergistic effect of the two active layers, the phenomenon of pulverization and falling of the negative electrode active layer caused by the volume expansion of the silicon-based composite active material in the charging and discharging process can be effectively overcome, the full charge rebound of the silicon-based negative electrode can be effectively inhibited in the charging and discharging process. In addition, the preparation method has controllable process conditions, and the prepared silicon-based negative electrode has stable performance.
The lithium ion battery of the invention contains the silicon-based negative electrode, so the lithium ion battery of the invention can apply the silicon-based negative electrode material with high gram capacity, and has stable cycle performance, long service life and high safety performance.
Drawings
The invention will be further described with reference to the accompanying drawings and examples, in which:
fig. 1 is a process step diagram of a silicon-based negative electrode preparation method according to an embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The parts by weight of the relevant components mentioned in the description of the embodiments of the present invention may not only refer to the content of each component but also to the weight ratio among the components, and therefore, it is within the scope of the disclosure of the description of the embodiments of the present invention to scale up or down the content of the relevant components according to the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiment of the present invention may be a unit of mass known in the chemical industry field, such as μ g, mg, g, and kg.
In one aspect, embodiments of the present invention provide a silicon-based negative electrode with stable structure and electrochemical performance and good cyclicity. The silicon-based negative electrode comprises a current collector and a negative active layer coated on the surface of the current collector.
The current collector comprises two opposite surfaces, the negative active layer is composed of a first active layer and a second active layer, the first active layer is coated on one side surface of the current collector, and the second active layer is coated on the other side surface of the current collector.
In one embodiment, the first active layer (dry powder) comprises the following components in parts by weight:
94.5 to 96.0 portions of silicon-based negative electrode material
1.0-1.5 parts of first conductive agent
2.5-3.0 parts of modified SBR binder (modified styrene-butadiene rubber binder)
In a specific embodiment, the silicon-based negative electrode material is a high-gram-capacity silicon-based negative electrode material, such as a silicon-based negative electrode material containing silicon monoxide or a silicon-based negative electrode material containing pure silicon. Wherein, the weight content of the inferior silicon in the silicon-based cathode material of the inferior silicon oxide is not less than 5 percent, and the weight content of the pure silicon in the silicon-based cathode material containing the pure silicon is not less than 3 percent. For example, in a specific embodiment, the silicon-based negative electrode material is silicon oxide + artificial graphite, that is, the silicon oxide + artificial graphite is obtained by mixing synthesized silicon oxide and artificial graphite; or carbon-coated nano silicon and artificial graphite, namely a silicon-based negative electrode material obtained by mixing carbon-coated nano silicon and artificial graphite. The silicon-based negative electrode material with high gram capacity is selected to have high gram capacity on one hand and relatively small volume expansion rate on the other hand. This can assist the negative active layer to further improve the structural stability and chemical stability of the negative electrode.
The first conductive agent may be a conventional conductive agent, and in one embodiment, the first conductive agent is at least one of aqueous CNTs, SP, and ketjen black. The conductive agent can be effectively dispersed among silicon-based negative electrode materials, so that the conductivity in the first active layer is improved, and the internal resistance of the electrode is reduced. In addition, the conductive agents have good water dispersibility and can be uniformly dispersed in the prepared slurry.
The modified SBR binder is dispersed on the surface of the silicon-based negative electrode material and the surface of the first conductive agent or filled among the components along with slurry, so that the silicon-based negative electrode material, the first conductive agent and other components have strong binding performance, the formed first active layer is integrated, and the structure stability is strong. Meanwhile, the bonding strength between the first active layer and the surface of the current collector is enhanced, the integral structure stability of the silicon-based negative electrode is provided, and the probability of poor pulverization phenomenon of the active layer due to volume expansion in the charging and discharging process is reduced. And the modified SBR binder has lower mobility in the slurry coating process, thereby ensuring the uniformity of the effective components of the first active layer and the uniformity of the thickness and providing the quality uniformity of the silicon-based negative electrode of the embodiment. Meanwhile, the modified SBR binder also has better liquid retention performance, so that the full charge rebound of the silicon-based negative electrode can be effectively inhibited and the cycle performance of the silicon-based negative electrode can be improved in the charge and discharge processes. The full-electricity rebound refers to the thickness expansion rate of the negative pole piece in a full-electricity state, and is specifically calculated according to the following formula:
the full-electricity rebound is 100% × (full-electricity thickness of the negative pole piece after capacity grading-thickness of the negative pole piece after roll pair)/thickness of the negative pole piece after roll pair.
In a specific example, the modified SBR binder is commercially available from JSR, japan, specifically 104A manufactured by JSR, which 104A has a solids content of 45%. The modified SBR is characterized in that a hydrophilic group is added on a side chain of styrene-butadiene latex, the hydrophilic group is broken along with solvent evaporation in a coating process, and only a connecting group between silicon-based cathodes is reserved, so that the binding power between the silicon-based cathodes is enhanced, the mobility of the SBR is reduced, the uniformity of a first active layer is improved, and the liquid retention performance of the first active layer on electrolyte is improved.
In addition, if the slurry for forming the first active layer (dry powder) further contains a dispersant or other additives, the first active layer (dry powder) further contains corresponding nonvolatile additive components, for example, 0.5 to 1.0 part by weight of a dispersant. In one embodiment, the dispersant is, but is not limited to, sodium carboxymethyl cellulose.
In another embodiment, the second active layer (dry powder) comprises the following components in parts by weight:
in a specific embodiment, the silicon-based negative electrode material may be the same as the silicon-based negative electrode material in the first active layer, and may be a silicon-based negative electrode material with a high gram capacity, such as a silicon-based negative electrode material containing silicon oxide, or a silicon-based negative electrode material containing pure silicon. Wherein, the weight content of the inferior silicon in the silicon-based cathode material of the inferior silicon oxide is not less than 5 percent, and the weight content of the pure silicon in the silicon-based cathode material containing the pure silicon is not less than 3 percent. For example, in a specific embodiment, the silicon-based negative electrode material is silicon oxide + artificial graphite, that is, the silicon oxide + artificial graphite is obtained by mixing synthesized silicon oxide and artificial graphite; or carbon-coated nano silicon and artificial graphite, namely a silicon-based negative electrode material obtained by mixing carbon-coated nano silicon and artificial graphite. The silicon-based negative electrode material has high gram capacity on one hand and relatively low volume expansion rate on the other hand. This can assist the negative active layer to further improve the structural stability and chemical stability of the negative electrode.
The second conductive agent may be a conventional conductive agent, and in one embodiment, the second conductive agent is at least one of aqueous CNTs, SP, and ketjen black. The conductive agent can be effectively dispersed among silicon-based negative electrode materials, so that the conductivity in the first active layer is improved, and the internal resistance of the electrode is reduced. In addition, the conductive agents have good water dispersibility and can be uniformly dispersed in the prepared slurry.
The conventional non-modified SBR binder and the modified acrylic binder form a composite binder, so that the structural stability of the second active layer is improved, and a more stable SEI film can be formed in the second active layer in the first charging process. In one embodiment, the conventional non-modified SBR binder may be commercially available as is, e.g., optionally but not exclusively, a conventional non-modified SBR binder available from Gaobav, e.g., SD-6516 (49% solids). In another embodiment, the modified acrylic binder may be LA133 (15% solid content) commercially available as toyol, or LD150 (15% solid content) available as guangzhou haiyi. By adopting the conventional non-modified SBR binder and the modified acrylic binder to compound, the composite binder acts with a silicon-based material and a conductive agent, so that the structural stability of the second active layer is improved, and a more stable SEI film can be formed in the first charging process.
In addition, in order to allow the silicon-based negative electrode to have a high gram-capacity while having a stable structure, in a specific embodiment, the thickness of the first active layer is 95 μm to 105 μm. In another specific embodiment, the second active layer has a thickness of 95 μm to 105 μm.
In a specific embodiment, in each of the above silicon-based negative electrode embodiments, the current collector included in the silicon-based negative electrode may be a negative current collector commonly used in lithium ion batteries, such as a copper foil.
Therefore, the silicon-based negative electrode in each embodiment adopts the first active layer containing the modified SBR binder and the second active layer containing the conventional non-modified SBR binder and the modified acrylic binder composite binder, so that the structure is stable, the bad phenomenon that the active layers are pulverized and fall off due to volume expansion in the charging and discharging processes of the silicon-based negative electrode is avoided, the two active layers generate an electrochemical synergistic effect, the structural stability and the high gram capacity of the silicon-based negative electrode are obviously improved, and the full charge rebound of the silicon-based negative electrode can be effectively inhibited and the cycle performance of the silicon-based negative electrode can be improved in the charging and discharging processes.
On the other hand, the embodiment of the invention also provides a preparation method of the silicon-based negative electrode in the embodiment of the invention. In one embodiment, the process steps of the preparation method of the silicon-based negative electrode according to the embodiment of the present invention are shown in fig. 1, and the preparation method includes the following steps:
step S01, preparing a first active layer slurry: preparing a first active layer slurry according to components contained in the first active layer slurry and the component proportion thereof and a preparation method of the electrode slurry:
step S02, preparing second active layer slurry: preparing a second active layer slurry according to components contained in the second active layer slurry and the component proportion thereof and a preparation method of the electrode slurry;
step S03, coating a first active layer on one side of the surface of the current collector: coating the first active layer slurry on one surface of two oppositely-arranged surface negative current collectors, and drying to form a first active layer;
step S04, coating a second active layer on the other side of the surface of the current collector: and coating the second active layer slurry on the other surface of the negative current collector, and drying to form a second active layer.
Specifically, in step S01, as an embodiment of the present invention, the first active layer slurry includes the following components in parts by weight, and therefore, the first active layer slurry is an aqueous slurry:
the silicon-based negative electrode material, the first conductive agent and the modified SBR binder contained in the slurry of the first active layer are all as described above, and are not described herein again.
In order to improve the dispersibility of the first active layer slurry and the stability of the dispersion system, a dispersant may be further included in addition to the components contained in the first active layer slurry. In a specific embodiment, the dispersant may be 0.5 to 1.0 parts by weight of sodium carboxymethyl cellulose.
In addition, the first active layer slurry may further include a wetting agent or further include other additives that are beneficial to improve the performance of the slurry, based on the components included in the first active layer slurry, in a specific embodiment, the wetting agent is not limited to N-methylpyrrolidone (NMP), and the content may be 3.0 to 5.0 parts by weight, such as 4.0 parts by weight. The wetting agent can improve the wetting of the first conductive agent and the water solvent, so that the first conductive agent and the binder are better mixed, and the coating quality of the first active layer slurry is improved.
In one embodiment, the viscosity of the first active layer slurry is adjusted to 3000-.
In step S02, the second active layer slurry includes the following components in parts by weight, and thus the second active layer slurry is an aqueous slurry:
the silicon-based negative electrode material, the second conductive agent, the conventional non-modified SBR binder and the modified acrylic binder contained in the second active layer slurry in the silicon-based negative electrode according to the embodiment of the present invention are the same as those contained in the second active layer in the silicon-based negative electrode, and are not described herein again.
Similarly, in order to improve the dispersibility of the second active layer slurry and the stability of the dispersion system, a dispersant may be further included in addition to the components contained in the second active layer slurry. In a specific embodiment, the dispersant may be 0.5 to 1.0 parts by weight of sodium carboxymethyl cellulose.
In addition, on the basis of the components contained in the second active layer slurry, the second active layer slurry may further contain a wetting agent or further contain other components such as an auxiliary agent which is beneficial to improve the performance of the slurry, and in a specific embodiment, the wetting agent is not only N-methylpyrrolidone (NMP), and in addition, the content of the wetting agent may be 3.0 to 5.0 parts by weight, for example, 4.0 parts by weight. The wetting agent can improve the wetting of the second conductive agent and the hydrosolvent, so that the second conductive agent and the binder are better mixed, and the coating quality of the second active layer slurry is improved.
In one embodiment, the viscosity of the second active layer slurry is adjusted to 3000-3500mpa.s (23 ± 2 ℃) by the addition amount of water such as deionized water, so as to realize uniform coating of the second active layer slurry and ensure uniformity of the whole active layer.
The deionized water used as the solvent of the slurry in the first active layer slurry and the second active layer slurry may be other types of water used in electrode production or in laboratories, such as distilled water, etc., and it is used as the solvent in the present embodiment regardless of the type of water, and therefore, any other water used as a substitute for the deionized water contained in the first active layer slurry is within the scope of the present disclosure.
In addition, the step S01 and the step S02 have no sequence.
In the above step S03, the first active layer slurry is coated on the negative electrode current collector surface side, which may be, but not exclusively, coated according to a conventional coating process.
In one embodiment, the thickness of the first active layer formed by controlling the amount of the first active layer slurry applied is 95 μm to 105 μm. The thickness of the coating layer is controlled to play a synergistic effect with the second active layer in the step S04, so that the silicon-based negative electrode provided by the embodiment of the invention has high gram capacity and excellent structural stability and electrochemical performance.
The negative electrode current collector in step S03 may be a negative electrode current collector commonly used in lithium ion batteries, such as a copper foil.
The second active layer slurry coated on the other side of the surface of the negative current collector in the above step S04 may be, but is not limited to, coated according to a conventional coating process.
In one embodiment, the thickness of the second active layer formed by controlling the amount of the second active layer slurry applied is 95 μm to 105 μm. The thickness of the coating layer is controlled to play a synergistic effect with the second active layer in the step S03, so that the silicon-based negative electrode provided by the embodiment of the invention has high gram capacity and excellent structural stability and electrochemical performance.
It is needless to say that the method for manufacturing a silicon-based negative electrode according to the embodiment of the present invention further includes other conventional process steps of the pole piece, such as sheet production and the like, after the step S04. Before the sheet making, the pole piece processed in the steps S03 and S04 is subjected to a vacuum drying process. As an embodiment of the present invention, the drying conditions of the step S03 and the step S04 are 130 ℃ to 140 ℃ to remove the slurry solvent, etc. After the processing of step S03 and step S04, the pole piece is vacuum dried under the condition of 100 ℃ and 120 ℃, and the drying at the temperature should be sufficient, such as 8-10 hours.
Therefore, in the preparation method of the silicon-based negative electrode in the embodiment, the modified SBR binder is coated on the surface of one side of the negative current collector to be used as the binder of the silicon-based negative electrode material to prepare the aqueous slurry, and the conventional non-modified SBR binder and the modified acrylic acid binder are coated on the other side of the current collector to be used as the binder of the silicon-based negative electrode material to prepare the aqueous slurry. In addition, the preparation method of the embodiment has controllable process conditions, and the prepared silicon-based negative electrode has stable performance.
In another aspect, based on the silicon-based negative electrode and the preparation method thereof, embodiments of the present invention further provide a lithium ion battery. The structure of the lithium ion battery can be similar to the conventional structure of the lithium ion battery, wherein the negative electrode contained in the lithium ion battery is the silicon-based negative electrode of the embodiment of the invention described above or the silicon-based negative electrode prepared by the preparation method of the embodiment of the invention.
Thus, since the lithium ion battery of the embodiment of the invention contains the silicon-based negative electrode of the embodiment of the invention, the lithium ion battery of the embodiment of the invention is endowed with excellent electrochemical performance, for example, the lithium ion battery of the embodiment of the invention is endowed with the advantages of capability of effectively inhibiting full-charge rebound and excellent cycle performance of the silicon-based negative electrode of the embodiment, high safety performance, long service life and high gram capacity.
A number of embodiments of the above-described silicon-based negative electrodes and methods of making the same will now be provided to further illustrate the invention.
Example 1
The embodiment provides a silicon-based negative electrode and a preparation method thereof. The silicon-based negative electrode comprises a negative current collector and a negative active layer coated on the surface of the current collector, wherein the negative active layer is composed of a first active layer and a second active layer, the first active layer is coated on one side of the current collector, the second active layer is coated on the other side of the current collector, the first active layer contains a modified SBR binder, and the second active layer contains a conventional SBR binder and a modified acrylic acid binder composite binder.
The preparation method of the silicon-based negative electrode of the embodiment is as follows:
s11, preparing first active layer slurry:
95.0 parts by weight of silicon-based negative electrode, 1.5 parts by weight of CNTs (aqueous), 3.0 parts by weight of modified SBR binder, 0.5 parts by weight of CMC, 4.0 parts by weight of NMP and 140 parts by weight of deionized water are prepared into first active layer slurry.
S12, preparing second active layer slurry:
95.0 parts by weight of a silicon-based negative electrode, 1.5 parts by weight of CNTs (aqueous), 1.0 part by weight of a conventional non-modified SBR binder, 2.5 parts by weight of a modified acrylic binder, 4.0 parts by weight of NMP and 140 parts by weight of deionized water are prepared into first active layer slurry.
S13, coating the first active layer slurry on the surface of one side of a negative current collector, and drying to form a first active layer with the thickness of 95-105 microns;
s14, coating the second active layer slurry on the other side surface of the negative current collector, and drying to form a second active layer of 95-105 microns;
and S15, preparing the silicon-based negative electrode after subsequent conventional process treatment.
Comparative example 1
95.0 parts by weight of a silicon-based negative electrode, 1.5 parts by weight of CNTs (aqueous), 3.0 parts by weight of SBR (conventional non-modified SBR binder), 0.5 parts by weight of CMC, 4.0 parts by weight of NMP and 140 parts by weight of deionized water are prepared into slurry, and an active layer with the thickness of 95-105 mu m is formed on the surface coating of a negative current collector according to the coating method of the embodiment 1 to form the silicon-based negative electrode.
Example 2
The embodiment provides a silicon-based negative electrode and a preparation method thereof. The silicon-based negative electrode comprises a negative current collector and a negative active layer coated on the surface of the current collector, wherein the negative active layer is composed of a first active layer and a second active layer, the first active layer is coated on one side of the current collector, the second active layer is coated on the other side of the current collector, the first active layer contains a modified SBR binder, and the second active layer contains a conventional SBR binder and a modified acrylic acid binder composite binder.
The preparation method of the silicon-based negative electrode of the embodiment is as follows:
step S21, preparing first active layer slurry:
95.5 parts by weight of a silicon-based negative electrode, 1.0 part by weight of CNTs (aqueous), 3.0 parts by weight of a modified SBR binder, 0.5 part by weight of CMC, 4.0 parts by weight of NMP and 140 parts by weight of deionized water are prepared into first active layer slurry.
Step S22, preparing second active layer slurry:
95.5 parts by weight of a silicon-based negative electrode, 1.0 part by weight of CNTs (aqueous), 1.0 part by weight of a conventional non-modified SBR binder, 2.5 parts by weight of a modified acrylic binder, 4.0 parts by weight of NMP and 140 parts by weight of deionized water are prepared into first active layer slurry.
S23, coating the first active layer slurry on the surface of one side of a negative current collector, and drying to form a first active layer with the thickness of 95-105 microns;
s24, coating the second active layer slurry on the other side surface of the negative current collector, and drying to form a second active layer of 95-105 microns;
and S25, preparing the silicon-based negative electrode after subsequent conventional process treatment.
Comparative example 2
95.5 parts by weight of a silicon-based negative electrode, 1.0 part by weight of CNTs (aqueous), 3.0 parts by weight of SBR (conventional non-modified SBR binder), 0.5 part by weight of CMC, 4.0 parts by weight of NMP and 140 parts by weight of deionized water are prepared into slurry, and an active layer with the thickness of 95-105 mu m is formed on the surface coating of a negative current collector according to the coating method of the embodiment 1, so that the silicon-based negative electrode is formed.
Example 3
The embodiment provides a silicon-based negative electrode and a preparation method thereof. The silicon-based negative electrode comprises a negative current collector and a negative active layer coated on the surface of the current collector, wherein the negative active layer is composed of a first active layer and a second active layer, the first active layer is coated on one side of the current collector, the second active layer is coated on the other side of the current collector, the first active layer contains a modified SBR binder, and the second active layer contains a conventional SBR binder and a modified acrylic acid binder composite binder.
The preparation method of the silicon-based negative electrode of the embodiment is as follows:
step S31, preparing first active layer slurry:
95.0 parts by weight of silicon-based negative electrode, 1.2 parts by weight of CNTs (aqueous), 2.5 parts by weight of modified SBR binder, 0.8 parts by weight of CMC, 4.0 parts by weight of NMP and 140 parts by weight of deionized water are prepared into first active layer slurry.
Step S32, preparing second active layer slurry:
95.0 parts by weight of a silicon-based negative electrode, 1.2 parts by weight of CNTs (aqueous), 1.5 parts by weight of a conventional non-modified SBR binder, 2.3 parts by weight of a modified acrylic binder, 4.0 parts by weight of NMP and 140 parts by weight of deionized water are prepared into first active layer slurry.
S33, coating the first active layer slurry on the surface of one side of a negative current collector, and drying to form a first active layer with the thickness of 95-105 microns;
s34, coating the second active layer slurry on the other side surface of the negative current collector, and drying to form a second active layer of 95-105 microns;
and S35, preparing the silicon-based negative electrode after subsequent conventional process treatment.
Comparative example 3
95.0 parts by weight of a silicon-based negative electrode, 1.2 parts by weight of CNTs (aqueous), 3.0 parts by weight of SBR (conventional non-modified SBR binder), 0.8 parts by weight of CMC, 4.0 parts by weight of NMP and 140 parts by weight of deionized water are prepared into slurry, and an active layer with the thickness of 95-105 mu m is formed on the surface coating of a negative current collector according to the coating method of the embodiment 1, so that the silicon-based negative electrode is formed.
Electrochemical performance test
The silicon-based negative electrodes provided in examples 1 to 3 and the negative electrode sheets provided in comparative examples 1 to 3 were assembled into lithium ion batteries according to a conventional procedure with a positive electrode sheet, an electrolyte, and the like, and electrochemical performance tests were performed on each lithium ion battery as shown in the following table, wherein the lithium ions were the same as the positive electrode sheet, the electrolyte, and the like except for the negative electrode sheet. The test results are shown in the following table:
from the data, the battery containing the silicon-based negative electrode provided by the embodiment of the invention has the advantages of high gram capacity, stable cycle performance, low full-current rebound rate and relatively high capacity retention rate during low-temperature discharge. Therefore, the first active layer and the second active layer contained in the silicon-based negative electrode of the embodiment of the invention play an electrochemical synergistic effect in the working process of the electrode, effectively overcome the phenomenon of pulverization and shedding of the negative active layer caused by volume expansion of the silicon-based negative electrode material in the charging and discharging process, and have excellent structural stability, excellent cycle performance stability, low full-current rebound rate and other performances. Therefore, the lithium ion battery provided by the embodiment of the invention has the advantages of long service life, stable cycle performance and high safety performance, and effectively inhibits the full-charge rebound phenomenon.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (8)
1. A silicon-based negative electrode comprises a current collector, wherein the current collector comprises two oppositely arranged surfaces, a first active layer is coated on one surface, and a second active layer is coated on the other surface; wherein,
the first active layer comprises the following components in parts by weight:
94.5 to 96.0 portions of silicon-based negative electrode material
1.0-1.5 parts of first conductive agent
2.5-3.0 parts of modified SBR binder; wherein the modified SBR binder is 104A produced by JSR in Japan;
the second active layer comprises the following components in parts by weight:
2. the negative silicon-based electrode of claim 1, wherein: the thickness of the first active layer is 95-105 μm; and/or the thickness of the second active layer is 95 μm to 105 μm; and/or the first conductive agent or/and the second conductive agent is/are at least one of aqueous CNTs, SP and Ketjen black.
3. A method for preparing a silicon-based negative electrode is characterized in that: the method comprises the following steps:
preparing a first active layer slurry according to the following components contained in the first active layer slurry and the component proportion thereof and a preparation method of the electrode slurry, wherein the first active layer slurry comprises the following components in parts by weight:
preparing a second active layer slurry according to the components contained in the second active layer slurry and the component proportion thereof and the preparation method of the electrode slurry, wherein the second active layer slurry comprises the following components in parts by weight:
coating the first active layer slurry on one surface of two oppositely-arranged surface negative current collectors to form a first active layer;
and coating the second active layer slurry on the other surface of the negative current collector to form a second active layer.
4. The production method according to claim 3, characterized in that: the first active layer slurry and/or the second active layer slurry also contain 0.5-1.0 part of dispersant.
5. The method of claim 4, wherein: the dispersant is sodium carboxymethyl cellulose.
6. The production method according to any one of claims 3 to 5, characterized in that: controlling the amount of the first active layer slurry to be applied so that the first active layer is formed to have a thickness of 95 μm to 105 μm; and/or by controlling the amount of the second active layer slurry applied so that the thickness of the second active layer formed is 95 μm to 105 μm.
7. The production method according to any one of claims 3 to 5, characterized in that: the first conductive agent or/and the second conductive agent is/are at least one of aqueous CNTs, SP and Ketjen black.
8. A lithium ion battery comprising a negative electrode, characterized in that: the negative electrode is a silicon-based negative electrode as defined in claim 1 or 2 or prepared by the preparation method as defined in any one of claims 3 to 7.
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