CN108598361A - A kind of anode plate for lithium ionic cell and preparation method thereof, lithium ion battery - Google Patents
A kind of anode plate for lithium ionic cell and preparation method thereof, lithium ion battery Download PDFInfo
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- CN108598361A CN108598361A CN201810475572.3A CN201810475572A CN108598361A CN 108598361 A CN108598361 A CN 108598361A CN 201810475572 A CN201810475572 A CN 201810475572A CN 108598361 A CN108598361 A CN 108598361A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
- H01M4/662—Alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of anode plate for lithium ionic cell and preparation method thereof, lithium ion batteries, belong to technical field of lithium ion.The anode plate for lithium ionic cell of the present invention, including collector, the collection liquid surface are disposed with cu-sn alloy coating and negative electrode material layer from inside to outside.The preparation method of the anode plate for lithium ionic cell of the present invention, includes the following steps：Collector is placed in electroplate liquid and carries out plating and forms cu-sn alloy coating in collection liquid surface, composite current collector is made；Contain copper ion and tin ion in the electroplate liquid, the molar ratio of the copper ion and tin ion is 1.2 6：1‑5；Negative electrode slurry is coated in composite current collector surface obtained, it is dry to get.For the anode plate for lithium ionic cell of the present invention in charge and discharge process, the volume expansion of copper-tin alloy can carry out a degree of alleviation by negative electrode material layer, and avoiding copper-tin alloy volume expansion leads to destruction to battery structure.
Description
Technical field
The present invention relates to a kind of anode plate for lithium ionic cell and preparation method thereof, lithium ion batteries, belong to lithium ion battery
Technical field.
Background technology
With the rapid development of the industries such as new-energy automobile, electronic equipment, people are close to capacity, the energy of lithium ion battery
Degree, safety and service life are proposed increasingly higher demands.In order to improve the capacity and energy density of battery, effectively
Approach is to improve the capacity of electrode material.But current negative material such as graphite, capacity already close to theoretical specific capacity,
Room for promotion is limited.
Tin base alloy anode material is cheap, good conductivity, has no toxic side effect and processing performance is good, and Sn and Li can be with
Tin lithiumation object is formed, there is very high lithium storage content, theoretical specific capacity is up to 994mAh/g, as lithium ion battery negative material
With great potential.But volume expansion of the tin in battery charge and discharge process is up to 400% so that battery material is easy powder
Change and falls off from collector.
Kamash alloy is deposited on collection liquid surface, such as Publication No. generally by electro-plating method in the prior art
The Chinese invention patent of CN1974869A discloses a kind of preparation method of Sn-Cu alloy material for negative pole of lithium ion cell, passes through
Copper sheet is electroplated in electroplate liquid and forms coating, obtains copper-tin alloy.
Kamash alloy is prepared by electrochemical deposition method, has many advantages, such as surface uniform and delicate, simple for process.But this
Copper-tin alloy prepared by electrochemical deposition method is planted, the volume expansion in charge and discharge process is still more serious, influences following for battery
Ring performance.
Invention content
The purpose of the present invention is to provide a kind of negative electrode of lithium ion battery that can weaken kamash alloy volume expansion influence
Piece.
The present invention also aims to provide a kind of preparation method of above-mentioned anode plate for lithium ionic cell.
The present invention also aims to provide a kind of lithium ion battery.
To achieve the above object, the technical solution of anode plate for lithium ionic cell of the invention is：
A kind of anode plate for lithium ionic cell, including collector, the collection liquid surface are disposed with copper and tin from inside to outside
Alloy layer and negative electrode material layer.
One layer of copper-tin alloy plating is provided between the collector and negative electrode material layer of the anode plate for lithium ionic cell of the present invention
Layer, in charge and discharge process, the volume expansion of copper-tin alloy can carry out a degree of alleviation by negative electrode material layer, avoid
Copper-tin alloy volume expansion leads to the destruction to battery structure.
Tin in cu-sn alloy coating has higher capacity, can increase the capacity of negative plate to a certain extent.And
Using cu-sn alloy coating, when coating can be utilized to deposit the characteristics of, improves alloy-layer in the binding force of collection liquid surface, avoids
Tin layers falling off from collection liquid surface.Negative electrode material layer is arranged in cu-sn alloy coating surface, being capable of balanced negative material and tin
Capacity.
After collection liquid surface forms cu-sn alloy coating, particle deposits when cu-sn alloy coating surface still maintains electricity
When surface topography, there is the rough surface that is formed by fine and closely woven metallic particles in coating surface, on the one hand can be coarse using its
Surface make the contact good degree between negative electrode active material and collector and then improve negative electrode material layer and coating and afflux
On the other hand electric conductivity between body can utilize coarse surface to improve the knot between negative electrode material layer and coating and collector
With joint efforts.
The molar ratio of copper and tin is 1-6 in the cu-sn alloy coating:1-5.5.Preferably 3.5-6:4.5-5.5.
The negative electrode material layer includes negative electrode active material, conductive agent, binder, the negative electrode active material, conductive agent,
The mass ratio of binder is 80-95:0.5-10:2-15.
The negative electrode active material is graphite.The graphite is artificial graphite or natural graphite.The stabilization of graphite material
Performance is enough to play certain inhibiting effect to volume expansion of the cu-sn alloy coating in charge and discharge process.The conductive agent is SP
Or CNTs.The binder is one or two kinds of in CMC, SBR, PVDF.Preferably, binder includes CMC and SBR.Institute
The mass ratio for stating CMC and SBR is 1.5-4:3-9.
The collector is copper foil.When using copper as collector, copper-tin alloy can also pass through the copper and collection in alloy
The good combination of fluid improves the binding force between coating and collector, avoids falling off for coating.The collector is smooth surface copper
Foil, hair surface copper foil or porous copper foil.The porous copper foil is 3D porous copper foils.The porosity of porous copper foil is 50%-90%.
The thickness of the cu-sn alloy coating and collector ratio is 0.05-0.5:1-1.5.The negative electrode material layer, copper and tin
Alloy layer, collector thickness ratio be 6-30:0.05-0.5:1-1.5.When copper foil is porous copper foil, copper-tin alloy is born
Carrying capacity is 0.01-0.05g/cm2。
The technical solution of preparation method of the anode plate for lithium ionic cell of the present invention is：
A kind of preparation method of above-mentioned anode plate for lithium ionic cell, includes the following steps：
1) collector is placed in electroplate liquid and carries out plating and forms cu-sn alloy coating in collection liquid surface, be made compound
Collector；Contain copper ion and tin ion in the electroplate liquid, the molar ratio of the copper ion and tin ion is 1.2-6：1-5；
2) negative electrode slurry is coated in composite current collector surface made from step 1), it is dry to get.
The anode plate for lithium ionic cell preparation method of the present invention deposits one layer of copper and tin using electrodeposition process and closes on a current collector
Layer gold, then over the alloyed layer by negative electrode slurry coating, negative plate takes into account the copper-tin alloy layer of high power capacity and the stone of high stability
Ink, had both improved the capacity of pole piece, also solved the problems, such as that tin-base active substance easily falls off from collector in charge and discharge process.
The anode plate for lithium ionic cell preparation process of the present invention is simple, easy to operate, cost-effective, and production efficiency is high.
The current density being electroplated described in step 1) is 0.5-20A/dm2.The time of the plating is 5-30min.Voltage
Ranging from 5-30V.Temperature when plating is 20-50 DEG C.Temperature when plating refers to the temperature of electroplate liquid.
Plating described in step 1) is constant pressure plating or constant current plating.
When plating is constant pressure plating, the ranging from 0.5-20A/dm of electric current2.In electroplating process, electric current can be with electricity
The plating time increases and tapers into.
When plating is constant current plating, the ranging from 5-30V of voltage.
The preparation method of electroplate liquid includes the following steps in step 1)：Mantoquita, pink salt are added to the water, are uniformly mixed i.e.
.The pink salt is sodium stannate or stannous chloride.Mantoquita is copper sulphate or copper chloride.
A concentration of 0.1-0.5mol/L of the pink salt in electroplate liquid.A concentration of 0.12-0.6mol/ of the mantoquita in electroplate liquid
L。
Electroplate liquid described in step 1) includes additive.A concentration of 0.5-30g/L of the additive in electroplate liquid.
The additive is lauryl sodium sulfate, neopelex, triethanolamine, polyether polyol, poly- second
Any one or the combination of several of them in glycol, gelatin, glucose, methoxy polyoxyethylene ether, op-10.The polyethylene glycol
Preferably polyethylene glycol 400.
Preferably, additive is lauryl sodium sulfate, neopelex, triethanolamine, polyether polyol, gathers
The combination of any one or a few and gelatin in ethylene glycol, glucose, methoxy polyoxyethylene ether, op-10.Further preferably
, additive is lauryl sodium sulfate, neopelex, triethanolamine, polyether polyol, polyethylene glycol, grape
Arbitrary two kinds in sugar, methoxy polyoxyethylene ether, op-10 with the combination of gelatin.
Electroplate liquid described in step 1) includes complexant for electroplating.A concentration of 200- of the complexant for electroplating in electroplate liquid
250g/L。
The complexant for electroplating is in pyrophosphate, sulfate, phosphate, citrate, diethanol amine, triethanolamine
Any one or the combination of several of them.Preferably, complexant for electroplating is sulfate, phosphate, citrate, diethanol amine, three second
The mixture of any one and pyrophosphate in hydramine.The mass ratio of the two is 1:3-22.
Specifically, the complexant for electroplating is potassium pyrophosphate, calgon, sodium citrate, diethanol amine, triethanolamine
In any one or several combinations.
Collector described in step 1) is copper foil.The collector is shiny copper foil, hair surface copper foil or porous copper foil.Institute
It is 3D porous copper foils to state porous copper foil.The porosity of porous copper foil is 50%-90%.
The collector is surface-treated before being placed in electroplate liquid.The surface treatment is supersound process, at electrolysis
The combination of one or more of reason, acidleach processing.After surface treatment, copper foil surface can be made to form ideal combination interface,
When plating, be conducive to electroplated layer collection liquid surface deposition.
Preferably, the surface treatment is first to carry out supersound process or electrolysis processing, then carries out acidleach processing again.
The acid of the acidleach processing is one kind in hydrochloric acid, sulfuric acid.A concentration of 0.05-0.2mol/ of the acid of acidleach processing
L.The time of acidleach processing is 1-2min.Electrolysis processing is electrolysed in solution of sodium bisulfite.The current density of electrolysis
For 0.05-0.2A/dm2。
Negative electrode slurry described in step 2) includes negative electrode active material, conductive agent, binder.The conductive agent be SP or
CNTs.The binder is one or two kinds of in CMC, SBR, PVDF.Preferably, binder includes CMC and SBR.It is described
The mass ratio of CMC and SBR is 1.5-4:3-9.Negative electrode slurry is to mix negative electrode active material, conductive agent, binder with solvent
It is obtained after uniformly.The negative electrode active material is graphite.Preferably, the graphite is artificial graphite or natural graphite.
Dry temperature is 105-120 DEG C in step 2).The dry time is 10-30min.
The technical solution of lithium ion battery of the present invention is：
A kind of lithium ion battery, including positive plate, negative plate, the negative plate are above-mentioned anode plate for lithium ionic cell.
The beneficial effects of the invention are as follows：
The collector with cu-sn alloy coating itself used in the anode plate for lithium ionic cell of the present invention has capacity, energy
Enough utilize the high capacity characteristics of kamash alloy, moreover it is possible to which it is firm to be combined using cu-sn alloy coating and collector, avoids kamash alloy
It falls off from collector.
Negative plate produced by the present invention has the characteristics that high-energy density, active material are firmly combined in collection liquid surface,
The negative plate has taken into account the high power capacity feature of kamash alloy material and the high stability feature of graphite cathode material, solves and is filling
Kamash alloy is since volume expansion is to the destruction problem of battery structure in discharge process.
Description of the drawings
Fig. 1 be embodiment 1 in composite current collector on cu-sn alloy coating XRD spectrum；
Fig. 2 is monolithic soft bag lithium ionic cell made from anode plate for lithium ionic cell using the present invention.
Specific implementation mode
Technical scheme of the present invention is described further with reference to specific embodiment.
Embodiment 1
The anode plate for lithium ionic cell of the present embodiment includes composite current collector and bearing coated in composite current collector surface
The thickness of pole material layer, the negative electrode material layer per one side is 60 μm；Negative electrode material layer includes negative electrode active material graphite, conductive agent
SP, binder, negative electrode active material graphite, conductive agent SP, binder mass ratio be 93:1:6, binder is 2 by mass ratio:
4 CMC and SBR mixing composition；Graphite is artificial graphite；Composite current collector is lithium ion battery composite current collector, lithium ion
Battery composite current collector includes copper foil of affluxion body and the cu-sn alloy coating for being attached to two surfaces of collector, copper-tin alloy
The molar ratio of copper and tin element is 6 in coating:5；Copper foil is shiny copper foil, and the thickness of copper foil is 12 μm；Copper foil is per one side
On cu-sn alloy coating thickness be 0.5 μm.
The preparation method of the anode plate for lithium ionic cell of the present embodiment includes the following steps：
1) it takes copper chloride, stannous chloride, complexing agent potassium pyrophosphate to be added to the water, is uniformly mixed and obtains premixed solution；Pre-
In miscible fluid, a concentration of 0.12mol/L of copper chloride, a concentration of 0.1mol/L of stannous chloride, a concentration of 200g/ of complexing agent
L；
2) additive gelatin and glucose are added in the premixed solution obtained into step 1), is uniformly mixed, obtains electroplate liquid；
In electroplate liquid, the additive amount of gelatin is 0.1g/L, and the additive amount of glucose is 0.5g/L；
3) it by collector shiny copper foil, is put into the dilute hydrochloric acid solution of a concentration of 0.1mol/L, impregnates 2min, taking-up water
Washing, the collector after must being surface-treated；
4) electroplate liquid made from step 2) is added in electroplating bath, the collector after surface treatment that step 3) obtains is put
Enter and be electroplated in the electroplate liquid of electroplating bath, composite current collector is made；Plating conditions are：Plating is that constant current is electroplated, current density
For 0.5A/dm2, electroplating time 10min, electroplating temperature is 30 DEG C；
5) by negative electrode active material artificial graphite, conductive agent SP, binder, deionized water mixing is added according to aforementioned proportion
Uniformly obtained negative electrode slurry；
6) above-mentioned composite current collector is taken, negative electrode slurry made from step 5) is coated in the surface of composite current collector, 110
DEG C dry 0.5h to get.
The lithium ion battery of the present embodiment includes positive plate, negative plate, diaphragm, electrolyte, and negative plate is above-mentioned lithium ion
Battery cathode sheet；The active material that positive plate is is NCM ternary materials, and diaphragm is celgard 2400；In electrolyte, solvent
EC/EMC/DMC=1:1:1 (w/w/w), LiPF6A concentration of 1mol/L, the VC containing 1wt% in electrolyte.
Embodiment 2
The anode plate for lithium ionic cell of the present embodiment includes composite current collector and bearing coated in composite current collector surface
The thickness of pole material layer, the negative electrode material layer per one side is 80 μm；Negative electrode material layer includes negative electrode active material graphite, conductive agent
CNTs, binder, negative electrode active material graphite, conductive agent CNTs, binder mass ratio be 90:2:8, binder PVDF；
Graphite is artificial graphite；Composite current collector is lithium ion battery composite current collector, and lithium ion battery includes with composite current collector
Copper foil of affluxion body and the cu-sn alloy coating for being attached to two surfaces of collector, copper and tin element in cu-sn alloy coating
Molar ratio be 6:5；Copper foil is hair surface copper foil, and the thickness of copper foil is 9 μm；The thickness of cu-sn alloy coating in the every one side of copper foil
It is 1.5 μm.
The preparation method of the anode plate for lithium ionic cell of the present embodiment includes the following steps：
1) it takes copper sulphate, stannous chloride, complexing agent potassium pyrophosphate to be added to the water, is uniformly mixed and obtains premixed solution；Pre-
In miscible fluid, a concentration of 0.6mol/L of copper sulphate, a concentration of 0.5mol/L of stannous chloride, a concentration of 240g/ of complexing agent
L；
2) additive gelatin and polyethylene glycol 400 are added in the premixed solution obtained into step 1), is uniformly mixed, obtains electric
Plating solution；In electroplate liquid, a concentration of 0.05g/L of additive gelatin, a concentration of 2mL/L of polyethylene glycol 400；
3) it by collector hair surface copper foil, is put into the dilution heat of sulfuric acid of a concentration of 0.05mol/L, impregnates 2min, take out and use
Water washing, the collector after must being surface-treated；
4) electroplate liquid made from step 2) is added in electroplating bath, the collector after surface treatment that step 3) obtains is put
Enter and is electroplated to get composite current collector in the electroplate liquid of electroplating bath；Plating conditions are：Plating is that constant current is electroplated, current density
For 1.0A/dm2, electroplating time 20min, electroplating temperature is 35 DEG C；
5) negative electrode active material artificial graphite, conductive agent CNTs, binder are added according to aforementioned proportion in solvent NMP,
It is uniformly mixed obtained negative electrode slurry；
6) above-mentioned composite current collector is taken, negative electrode slurry made from step 5) is coated in the surface of composite current collector, 110
DEG C dry 1h to get.
The lithium ion battery of the present embodiment includes positive plate, negative plate, diaphragm, electrolyte, and negative plate is above-mentioned lithium ion
Battery cathode sheet；The active material of positive plate is NCM ternary materials, diaphragm Celgard2400；In electrolyte, solvent EC/
EMC/DMC=1:1:1 (w/w/w), LiPF6A concentration of 1mol/L, the VC containing 1wt% in electrolyte.
Embodiment 3
The anode plate for lithium ionic cell of the present embodiment includes composite current collector and bearing coated in composite current collector surface
The thickness of pole material layer, the negative electrode material layer per one side is 80 μm；Negative electrode material layer includes negative electrode active material graphite, conductive agent
CNTs, binder, negative electrode active material graphite, conductive agent CNTs, binder mass ratio be 85:2:13, binder is by quality
Than being 4:9 CMC and SBR mixing composition；Graphite is artificial graphite；Composite current collector is lithium ion battery composite current collector,
Lithium ion battery composite current collector includes copper foil of affluxion body and the cu-sn alloy coating for being attached to two surfaces of collector, copper
The molar ratio of copper and tin element is 6 in tin alloy coat：5；Copper foil is 3D porous copper foils, and the porosity of copper foil is 70%,
The load capacity of copper-tin alloy is 0.034g/cm on porous copper foil2。
The preparation method of the anode plate for lithium ionic cell of the present embodiment includes the following steps：
1) it takes copper chloride, sodium stannate, complexing agent potassium pyrophosphate and calgon to be added to the water, is uniformly mixed and is premixed
Solution；In premixed solution, a concentration of 0.3mol/L of copper chloride, a concentration of 0.3mol/L of sodium stannate, complexing agent pyrophosphoric acid
A concentration of 180g/L of potassium, a concentration of 60g/L of calgon；
2) additives polyethylene glycol 400, gelatin, op-10 are added in the premixed solution obtained into step 1), mixing is equal
It is even, obtain electroplate liquid；In electroplate liquid, a concentration of 1mL/L of polyethylene glycol 400, a concentration of 0.05g of gelatin, op-10's is a concentration of
0.2mL/L；
3) by collector 3D porous copper foils, 2min is impregnated in supersound process 3min, the 0.2mol/L dilute hydrochloric acid of 50W power,
Collector after must being surface-treated；
4) electroplate liquid made from step 2) is added in electroplating bath, the collector after surface treatment that step 3) obtains is put
Enter and is electroplated to get composite current collector in the electroplate liquid of electroplating bath；Plating conditions are：Plating is that constant current is electroplated, current density
For 10A/dm2, electroplating time 6min, electroplating temperature is 35 DEG C；
5) solvent deionization is added according to aforementioned proportion in negative electrode active material artificial graphite, conductive agent CNTs, binder
In water, it is uniformly mixed obtained negative electrode slurry；
6) above-mentioned composite current collector is taken, negative electrode slurry made from step 5) is coated in the surface of composite current collector, 110
DEG C dry 0.5h to get.
The lithium ion battery of the present embodiment includes positive plate, negative plate, diaphragm, electrolyte, and negative plate is above-mentioned lithium ion
Battery cathode sheet；The active material of positive plate is NCM ternary materials, diaphragm Celgard2400；In electrolyte, solvent EC/
EMC/DMC=1:1:1 (w/w/w), LiPF6A concentration of 1mol/L, the VC containing 1wt% in electrolyte.
Embodiment 4
The anode plate for lithium ionic cell of the present embodiment includes composite current collector and bearing coated in composite current collector surface
The thickness of pole material layer, the negative electrode material layer per one side is 85 μm；Negative electrode material layer includes negative electrode active material graphite, conductive agent
SP, binder, negative electrode active material graphite, conductive agent, binder mass ratio be 94.5:1:4.5, binder 1.5:3
CMC and SBR；Graphite is artificial graphite；Composite current collector is lithium ion battery composite current collector, lithium ion battery Composite Set
Fluid includes copper foil of affluxion body and the cu-sn alloy coating for being attached to two surfaces of collector, copper in cu-sn alloy coating
Molar ratio with tin element is 6:5；Copper foil is hair surface copper foil, and the thickness of copper foil is 12 μm；Copper-tin alloy in the every one side of copper foil
The thickness of coating is 3 μm.
The preparation method of the anode plate for lithium ionic cell of the present embodiment includes the following steps：
1) it takes copper chloride, stannous chloride, complexing agent potassium pyrophosphate and triethanolamine to be added to the water, is uniformly mixed and is premixed
Solution；In premixed solution, a concentration of 0.24mol/L of copper chloride, a concentration of 0.3mol/L of stannous chloride tin, potassium pyrophosphate
Additive amount be 220g/L, the additive amount of triethanolamine is 10g/L；
2) additive glucose and neopelex are added in the premixed solution obtained into step 1), mixing is equal
It is even, obtain electroplate liquid；In electroplate liquid, the additive amount of glucose is 0.8g/L, and the additive amount of neopelex is 0.5g/L；
3) by collector hair surface copper foil, the 0.05A/dm in the solution of sodium bisulfite of 1mol/L2Under conditions of Constant Electric Current
Solution processing 2min, then washing are dried, and impregnate the collector after 1min must be surface-treated using the dilute hydrochloric acid of 0.1mol/L；
4) electroplate liquid made from step 2) is added in electroplating bath, the collector after surface treatment that step 3) obtains is put
Enter and is electroplated to get composite current collector in the electroplate liquid of electroplating bath；Plating conditions are：Plating is that constant current is electroplated, current density
For 1.2A/dm2, electroplating time 15min, electroplating temperature is 35 DEG C；
5) solvent deionized water is added according to aforementioned proportion in negative electrode active material artificial graphite, conductive agent SP, binder
In, it is uniformly mixed obtained negative electrode slurry；
6) above-mentioned composite current collector is taken, negative electrode slurry made from step 5) is coated in the surface of composite current collector, 110
DEG C dry 0.5h to get.
The lithium ion battery of the present embodiment includes positive plate, negative plate, diaphragm, electrolyte, and negative plate is above-mentioned lithium ion
Battery cathode sheet；The active material of positive plate is NCM ternary materials, diaphragm Celgard2400；In electrolyte, solvent EC/
EMC/DMC=1:1:1 (w/w/w), LiPF6A concentration of 1mol/L, the VC containing 1wt% in electrolyte.
Comparative example 1
It is graphite, conductive agent SP, binder with reference to the negative electrode active material in embodiment 1, negative electrode active material graphite,
Conductive agent SP, binder mass ratio be 93:1:6, binder is 2 by mass ratio:4 CMC and SBR mixing composition；Graphite is
Artificial graphite.
Using hair surface copper foil as collector, with reference to the method in embodiment 1, negative electrode slurry is directly coated in hair surface copper foil table
Face, and prepare anode plate for lithium ionic cell and lithium ion battery.
Comparative example 2
Using hair surface copper foil as collector, with reference to the plating liquid making method sum aggregate fluid treatment method of embodiment 1, increase electricity
Current density is 2.0A/dm2, extend electroplating time to 45min, the composite material of 28 μ m-thick alloy-layers obtained, with this composite material
Lithium ion battery is prepared for negative plate.
Test example
(1) copper-tin alloy on the composite current collector surface in Example 1 carries out XRD tests, test result such as Fig. 1 institutes
Show.
As can be seen from Figure 1 the main component of alloy-layer is Cu6Sn5。
(2) anode plate for lithium ionic cell in Example 1-4 and comparative example, positive plate, N/ are prepared with NCM ternary materials
P designs 1.05, are made monolithic soft bag lithium ionic cell, as shown in Figure 2.
Battery is melted into accordance with the following steps：
1) it is shelved for 24 hours in 40 DEG C of baking ovens；
2) 0.1C charges to 4.3V；
3) 0.1C is discharged to 2.7V；
4) 0.1C charges to 4.3V；
5) 0.2C is discharged to 2.7V；
6) 0.1C charges to 4.3V；
7) 0.2C is discharged to 2.7V.
Battery charging and discharging cycle performance is tested：
The charge-discharge performance of lithium ion battery is tested in accordance with the following steps：
1) 0.2C charges to 4.3V；
2) 0.5C is discharged to 2.7V；
1) and 2) 3) repeat.
Test result is as shown in table 1.
Performance of lithium ion battery made from anode plate for lithium ionic cell in 1 embodiment 1-4 of table and comparative example
As shown in Table 1, the internal resistance of cell made from anode plate for lithium ionic cell of the invention reduces, by 100 circulation volumes
Conservation rate is generally 90% or more, the cathode piece performance prepared very close to conventional method in comparative example 1, in comparative example 2 directly
Decay in negative plate discharge process prepared by electrodeposition process very fast, declines to a great extent by 50 circulation volumes, it was demonstrated that of the invention
Circulating battery stability prepared by combination electrode plate is preferable.
Claims (10)
1. a kind of anode plate for lithium ionic cell, including collector, which is characterized in that the collection liquid surface is set successively from inside to outside
It is equipped with cu-sn alloy coating and negative electrode material layer.
2. anode plate for lithium ionic cell according to claim 1, it is characterised in that：Copper and tin in the cu-sn alloy coating
Molar ratio be 1-6:1-5.5.
3. anode plate for lithium ionic cell according to claim 1, it is characterised in that：The negative electrode material layer includes that cathode is lived
Property substance, conductive agent, binder, the negative electrode active material, conductive agent, binder mass ratio be 80-95:0.5-10:2-
15。
4. anode plate for lithium ionic cell according to claim 1, it is characterised in that：The collector is copper foil.
5. anode plate for lithium ionic cell according to claim 1, it is characterised in that：The cu-sn alloy coating and collector
Thickness ratio be 0.05-0.5:1-1.5.
6. a kind of preparation method of anode plate for lithium ionic cell as described in claim 1, it is characterised in that：Including walking as follows
Suddenly：
1) collector is placed in electroplate liquid and carries out plating and forms cu-sn alloy coating in collection liquid surface, composite current collecting is made
Body；Contain copper ion and tin ion in the electroplate liquid, the molar ratio of the copper ion and tin ion is 1.2-6：1-5.5；
2) negative electrode slurry is coated in composite current collector surface made from step 1), it is dry to get.
7. the preparation method of anode plate for lithium ionic cell according to claim 6, it is characterised in that：It is electric described in step 1)
The current density of plating is 0.5-20A/dm2。
8. the preparation method of anode plate for lithium ionic cell according to claim 6, it is characterised in that：It is electric described in step 1)
The time of plating is 5-30min.
9. the preparation method of anode plate for lithium ionic cell according to claim 6, it is characterised in that：The collector is being set
In electroplate liquid before be surface-treated, it is described surface treatment be supersounds process, electrolysis processing, acidleach handle in one kind or
Several combinations.
10. a kind of lithium ion battery, including positive plate, negative plate, it is characterised in that：The negative plate is such as claim 1 institute
The anode plate for lithium ionic cell stated.
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| CN110767956A (en) * | 2019-11-02 | 2020-02-07 | 河南电池研究院有限公司 | Method for stripping lithium ion battery electrode plate material and current collector |
| CN113929188A (en) * | 2020-06-29 | 2022-01-14 | 佛山市顺德区美的饮水机制造有限公司 | Electrode structure, purification structure and electrode preparation method |
| CN113991059A (en) * | 2021-11-09 | 2022-01-28 | 河南电池研究院有限公司 | Lithium ion battery negative pole piece and preparation method thereof |
| US20220181677A1 (en) * | 2020-12-03 | 2022-06-09 | Honda Motor Co., Ltd. | Lithium ion secondary battery |
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Application publication date: 20180928 |