CN103943861B - A kind of anode piece of lithium ion secondary battery and preparation method thereof and lithium rechargeable battery - Google Patents
A kind of anode piece of lithium ion secondary battery and preparation method thereof and lithium rechargeable battery Download PDFInfo
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- CN103943861B CN103943861B CN201310021519.3A CN201310021519A CN103943861B CN 103943861 B CN103943861 B CN 103943861B CN 201310021519 A CN201310021519 A CN 201310021519A CN 103943861 B CN103943861 B CN 103943861B
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- H01M4/00—Electrodes
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- 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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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
Embodiments provide a kind of anode piece of lithium ion secondary battery, it is made up of collector, positive electrode active materials, conductive agent and binding agent, containing transition metal in positive electrode active materials, acetylene compound that transiting metal surface has carbon number to be 2 ~ 10 by chemical bonds and derivant thereof, carbon number are one or more in the alkyl that mercaptan, sulfide, hydrogen phosphide and carbon number are 1 ~ 10 replacement phosphide of 1 ~ 10.The embodiment of the present invention overcomes the problem of the transition metal-catalyzed electrolyte generation oxidation Decomposition in prior art in anode active material of lithium ion secondary battery, thus improves lithium rechargeable battery cycle performance under 4.5V and above high voltage.The embodiment of the present invention additionally provides the preparation method of this anode piece of lithium ion secondary battery, and comprises the lithium rechargeable battery of this anode piece of lithium ion secondary battery.
Description
Technical field
The present invention relates to field of lithium ion battery, particularly relate to a kind of anode piece of lithium ion secondary battery and
Its preparation method and lithium rechargeable battery.
Background technology
Lithium ion battery is mainly made up of positive pole, negative pole, barrier film, shell and electrolyte, passes through Li+Embed
With abjection positive and negative electrode material carry out energy exchange a kind of can the high-energy battery of discharge and recharge, it is higher because having
Energy density, good cycle performance, the feature such as memory-less effect step into the sight line of people, and become
For researchers' focus of attention in recent years.
Present stage, when running voltage reaches 4.5V, electrolyte system will occur oxidation Decomposition, therefore the most mostly
The lithium rechargeable battery of number is difficult under 4.5V and above high voltage stable use.A reason among these
For: the transition metal (such as manganese, nickel and cobalt etc.) contained in positive electrode active materials has stronger catalysis and lives
Property (sees G.G.Amatucci etc., Surface treatments of Li1+xMn2-xO4spinels for improved
Elevated temperature performance, Solid State Ionics104 (1997) 13-25), these transition gold
Belong to catalytic electrolysis liquid system generation oxidation Decomposition, thus cause lithium rechargeable battery normally to use,
Lithium rechargeable battery cycle life under high pressure is drastically reduced.
Along with the extension in lithium ion battery applications field, the new application scenarios such as including the standby electricity in high temperature base station in recent years
Introducing, people propose higher expectation to lithium ion battery chemical property at high temperature.Such as,
Someone reports by adding the high sulfone class of antioxidation current potential, nitrile, ionic liquid class material as electrolyte
Solvent is to replace the most conventional carbonic ester, thus improves the running voltage of electrolyte to more than 5V, but
Their the less transfer rate that can reduce lithium ion in the electrolytic solution of electrical conductivity, their viscosity is relatively big, with
And they are poor to the wettability of electrode and barrier film, therefore they do not obtain actual application yet.Additionally, also
Someone report by add in the electrolytic solution can the high voltage additive of preferential oxidized decomposition at positive electrode surface
Form protective layer, thus intercept contacting of positive electrode active materials and electrolyte, and then avoid electrolyte oxidized
Decompose, but the high voltage additive types that can be applicable under 4.9V high voltage reported at present is considerably less, temporarily
Time be not also commercially used.
Summary of the invention
In view of this, embodiment of the present invention first aspect provides a kind of anode piece of lithium ion secondary battery, gram
Take the transition metal-catalyzed electrolyte generation oxygen in anode active material of lithium ion secondary battery in prior art
Change the problem decomposed, thus improve lithium rechargeable battery cycle performance under 4.5V and above high voltage.
Embodiment of the present invention second aspect provides the preparation method of this anode piece of lithium ion secondary battery.The present invention
The embodiment third aspect provides the lithium ion battery comprising this anode piece of lithium ion secondary battery.
First aspect, embodiments provides a kind of anode piece of lithium ion secondary battery, described lithium ion
Anode of secondary battery pole piece is made up of collector, positive electrode active materials, conductive agent and binding agent, described positive pole
Containing transition metal in active material, described transiting metal surface has the carbon number to be by chemical bonds
The acetylene compound of 2 ~ 10 and derivant thereof, carbon number are mercaptan, sulfide, hydrogen phosphide and the carbon of 1 ~ 10
Atomic number is one or more in the alkyl replacement phosphide of 1 ~ 10.
Wherein, positive electrode active materials can embed or deviate from lithium ion, preferred platform voltage in the embodiment of the present invention
It it is the positive electrode active materials of 4.5 ~ 5V.Preferably, positive electrode active materials is LiMxMn(2-x)O4, wherein M choosing
One or more in transition metal Ni, Co and Fe, 0≤x≤2.It is further preferred that positive electrode active materials
For xLi2MnO3(1-x)LiMO2, wherein one or more in transition metal Ni, Co and Mn of M,
0≤x≤1。
Carbon number is the acetylene compound of 2 ~ 10 and mercaptan, sulfur that derivant, carbon number are 1 ~ 10
Compound, hydrogen phosphide and carbon number are that one or more in the alkyl replacement phosphide of 1 ~ 10 pass through chemical bond
It is combined in transiting metal surface, covers the active site of transiting metal surface, so that transition metal
Lose catalytic oxidation activity.
Preferably, transiting metal surface by chemical bonds have acetylene, propine, hydrogen sulfide, hydrogen phosphide, three
One or more in methylphosphine and triethyl phosphine.
Preferably, collector is aluminium foil, nickel screen or aluminum-plastic composite membrane.
Preferably, conductive agent is acetylene black.
Preferably, binding agent is Kynoar (PVDF), butadiene-styrene rubber breast (SBR) or carboxymethyl cellulose
Sodium (CMC).
In the anode piece of lithium ion secondary battery that embodiment of the present invention first aspect provides, described positive-active material
In material, transiting metal surface has the molecule that transition metal can be made to lose catalytic oxidation activity by chemical bonds,
The active site making transiting metal surface is blanked thus loses the activity of catalysis oxidation, therefore solves
The problem that transition metal catalytic electrolysis liquid oxidation under high voltages in positive electrode active materials is decomposed, thus carry
High lithium rechargeable battery cycle performance under 4.5V and above high voltage.
Second aspect, embodiments provides the preparation method of a kind of anode piece of lithium ion secondary battery,
Comprise the following steps:
Take positive electrode active materials, conductive agent, binding agent and solvent, mix, stir, prepare anode sizing agent,
Containing transition metal in described positive electrode active materials；
Being coated with on a current collector by anode sizing agent, step subsequently also includes drying, rolling and is placed in gas gas
Atmosphere is shelved, described gas be carbon number be 2 ~ 10 acetylene compound and derivant, carbon number be
The alkyl that mercaptan, sulfide, hydrogen phosphide and carbon number are 1 ~ 10 of 1 ~ 10 replace the one in phosphide or
Several, described drying, rolling and be placed in the order shelved in gas atmosphere and do not limit, prepared lithium ion secondary is just
Pole pole piece.
Wherein, positive electrode active materials can embed or deviate from lithium ion, can be selected for platform electricity in the embodiment of the present invention
Pressure is the positive electrode active materials of 4.5 ~ 5V.Preferably, positive electrode active materials is LiMxMn(2-x)O4, wherein M
One or more in transition metal Ni, Co and Fe, 0≤x≤2.It is further preferred that positive-active material
Material is xLi2MnO3(1-x)LiMO2, wherein M one or several in transition metal Ni, Co and Mn
Kind, 0≤x≤1.
Carbon number is the acetylene compound of 2 ~ 10 and mercaptan, sulfur that derivant, carbon number are 1 ~ 10
Compound, hydrogen phosphide and carbon number are that one or more in the alkyl replacement phosphide of 1 ~ 10 pass through chemical bond
It is combined in transiting metal surface, covers the active site of transiting metal surface, so that transition metal
Lose catalytic oxidation activity.
Preferably, during gas is acetylene, propine, hydrogen sulfide, hydrogen phosphide, trimethyl-phosphine and triethyl phosphine
Plant or several.
Preferably, being placed in the time shelved in gas atmosphere is 0.1 ~ 24 hour.It is highly preferred that be placed in gas
The time shelved in atmosphere is 0.5 ~ 6 hour.
Preferably, gas is dry gas.
Preferably, collector is aluminium foil, nickel screen or aluminum-plastic composite membrane.
Preferably, conductive agent is acetylene black.
Preferably, binding agent is Kynoar (PVDF), butadiene-styrene rubber breast (SBR) or carboxymethyl cellulose
Sodium (CMC).
Preferably, solvent is N-Methyl pyrrolidone solution (nmp solution).
The preparation method of the anode piece of lithium ion secondary battery that embodiment of the present invention second aspect provides is compared often
For the preparation method of the anode piece of lithium ion secondary battery of rule, increase only step and " be placed in gas atmosphere
In shelve ", and " be placed in gas atmosphere and shelve " can dry before carry out, it is also possible to dry with
Carry out between rolling, it is also possible to carrying out after rolling, method is simple." it is being placed in gas atmosphere
Shelve " during, the site that gas molecule has catalysis active by chemical bond with transiting metal surface is combined,
Thus cover at transiting metal surface, i.e. occupy transiting metal surface and there is the site of catalysis activity make this
Site loses the activity of catalysis oxidation, therefore solves the transition metal in positive electrode active materials under high voltages
The problem that catalytic electrolysis liquid oxidation is decomposed, thus improve lithium rechargeable battery at 4.5V and above high voltage
Under cycle performance, and, prepare anode piece of lithium ion secondary battery be applicable to high voltage occasion.
The third aspect, embodiments provides a kind of lithium ion battery, including anode pole piece, negative pole pole
Sheet, barrier film, electrolyte and shell, described anode piece of lithium ion secondary battery is by collector, positive-active
Material, conductive agent and binding agent composition, containing transition metal in described positive electrode active materials, described transition gold
Acetylene compound that metal surface has carbon number to be 2 ~ 10 by chemical bonds and derivant, carbon number
It is in the alkyl that mercaptan, sulfide, hydrogen phosphide and carbon number are 1 ~ 10 replacement phosphide of 1 ~ 10
Plant or several.
The embodiment of the present invention third aspect provide lithium ion battery be applicable to high voltage occasion, 4.5V and with
There is under upper high voltage good cycle performance, in its preparation method, can be at prepared lithium rechargeable battery
Complete " be placed in gas atmosphere and shelve ", it is also possible to anode piece of lithium ion secondary battery is being cut into slices it before
Afterwards or complete making after core is placed in housing.
The advantage of the embodiment of the present invention will partly illustrate, and a part according to description is
It will be apparent that or can be known by the enforcement of the embodiment of the present invention.
Detailed description of the invention
The following stated is the preferred implementation of the embodiment of the present invention, it is noted that for the art
For those of ordinary skill, on the premise of without departing from embodiment of the present invention principle, it is also possible to make some changing
Entering and retouch, these improvements and modifications are also considered as the protection domain of the embodiment of the present invention.
Divide multiple embodiment that the embodiment of the present invention is further detailed below.Wherein, the present invention implements
Example is not limited to following specific embodiment.In the range of constant principal right, can change by suitable carrying out
Implement.
Embodiment of the present invention first aspect provides a kind of anode piece of lithium ion secondary battery, overcomes existing skill
In art, the transition metal-catalyzed electrolyte generation oxidation Decomposition in anode active material of lithium ion secondary battery asks
Topic, thus improve lithium rechargeable battery cycle performance under 4.5V and above high voltage.The present invention is real
Execute example second aspect and provide the preparation method of this anode piece of lithium ion secondary battery.The embodiment of the present invention
Three aspects provide the lithium ion battery comprising this anode piece of lithium ion secondary battery.
First aspect, embodiments provides a kind of anode piece of lithium ion secondary battery, described lithium ion
Anode of secondary battery pole piece is made up of collector, positive electrode active materials, conductive agent and binding agent, described positive pole
Containing transition metal in active material, described transiting metal surface has the carbon number to be by chemical bonds
The acetylene compound of 2 ~ 10 and derivant thereof, carbon number are mercaptan, sulfide, hydrogen phosphide and the carbon of 1 ~ 10
Atomic number is one or more in the alkyl replacement phosphide of 1 ~ 10.
Wherein, positive electrode active materials can embed or deviate from lithium ion, can be selected for platform electricity in the embodiment of the present invention
Pressure is the positive electrode active materials of 4.5 ~ 5V.Positive electrode active materials is LiMxMn(2-x)O4, wherein M was selected from
Cross one or more in W metal, Co and Fe, 0≤x≤2.Positive electrode active materials can also be
xLi2MnO3(1-x)LiMO2, wherein one or more in transition metal Ni, Co and Mn of M, 0
≤x≤1。
Carbon number is the acetylene compound of 2 ~ 10 and mercaptan, sulfur that derivant, carbon number are 1 ~ 10
Compound, hydrogen phosphide and carbon number are that one or more in the alkyl replacement phosphide of 1 ~ 10 pass through chemical bond
It is combined in transiting metal surface, covers the active site of transiting metal surface, so that transition metal
Lose catalytic oxidation activity.
Described transiting metal surface has acetylene, propine, hydrogen sulfide, hydrogen phosphide, trimethyl by chemical bonds
One or more in phosphine and triethyl phosphine.
Collector is aluminium foil, nickel screen or aluminum-plastic composite membrane.
Conductive agent is acetylene black.
Binding agent is Kynoar (PVDF), butadiene-styrene rubber breast (SBR) or sodium carboxymethyl cellulose (CMC).
In the anode piece of lithium ion secondary battery that embodiment of the present invention first aspect provides, described positive-active material
In material, transiting metal surface has the molecule that transition metal can be made to lose catalytic oxidation activity by chemical bonds,
The active site making transiting metal surface is blanked thus loses the activity of catalysis oxidation, therefore solves
The problem that transition metal catalytic electrolysis liquid oxidation under high voltages in positive electrode active materials is decomposed, thus carry
High lithium rechargeable battery cycle performance under 4.5V and above high voltage.
Second aspect, embodiments provides the preparation method of a kind of anode piece of lithium ion secondary battery,
Comprise the following steps:
Take positive electrode active materials, conductive agent, binding agent and solvent, mix, stir, prepare anode sizing agent,
Containing transition metal in described positive electrode active materials；
Being coated with on a current collector by anode sizing agent, step subsequently also includes drying, rolling and is placed in gas gas
Atmosphere is shelved, described gas be carbon number be 2 ~ 10 acetylene compound and derivant, carbon number be
The alkyl that mercaptan, sulfide, hydrogen phosphide and carbon number are 1 ~ 10 of 1 ~ 10 replace the one in phosphide or
Several, described drying, rolling and be placed in the order shelved in gas atmosphere and do not limit, prepared lithium ion secondary is just
Pole pole piece.
Wherein, positive electrode active materials can embed or deviate from lithium ion, can be selected for platform electricity in the embodiment of the present invention
Pressure is the positive electrode active materials of 4.5 ~ 5V.Positive electrode active materials is LiMxMn(2-x)O4, wherein M was selected from
Cross one or more in W metal, Co and Fe, 0≤x≤2.Positive electrode active materials can also be
xLi2MnO3(1-x)LiMO2, wherein one or more in transition metal Ni, Co and Mn of M, 0
≤x≤1。
Carbon number is the acetylene compound of 2 ~ 10 and mercaptan, sulfur that derivant, carbon number are 1 ~ 10
Compound, hydrogen phosphide and carbon number are that one or more in the alkyl replacement phosphide of 1 ~ 10 pass through chemical bond
It is combined in transiting metal surface, covers the active site of transiting metal surface, so that transition metal
Lose catalytic oxidation activity.
Gas is one or more in acetylene, propine, hydrogen sulfide, hydrogen phosphide, trimethyl-phosphine and triethyl phosphine.
Being placed in the time shelved in gas atmosphere is 0.1 ~ 24 hour.Specifically, it is placed in gas atmosphere and shelves
Time be 0.5 ~ 6 hour.
Gas is dry gas.
Collector is aluminium foil, nickel screen or aluminum-plastic composite membrane.
Conductive agent is acetylene black.
Binding agent is Kynoar (PVDF), butadiene-styrene rubber breast (SBR) or sodium carboxymethyl cellulose (CMC).
Solvent is N-Methyl pyrrolidone solution (nmp solution).
The preparation method phase of a kind of anode piece of lithium ion secondary battery that embodiment of the present invention second aspect provides
For preparation method than conventional anode piece of lithium ion secondary battery, increase only step and " be placed in gas
Atmosphere is shelved ", and " be placed in gas atmosphere and shelve " can dry before carry out, it is also possible to dry
Do and carry out between rolling, it is also possible to carrying out after rolling, method is simple." it is being placed in gas gas
Atmosphere is shelved " during, gas molecule has the site of catalysis activity by chemical bond and transiting metal surface
In conjunction with, thus cover at transiting metal surface, i.e. occupy transiting metal surface and there is the site of catalysis activity
Make this site lose the activity of catalysis oxidation, therefore solve the transition metal in positive electrode active materials at height
Under voltage catalytic electrolysis liquid oxidation decompose problem, thus improve lithium rechargeable battery 4.5V and more than
Cycle performance under high voltage, and, the anode piece of lithium ion secondary battery prepared is applicable to high voltage field
Close.
The third aspect, embodiments provides a kind of lithium ion battery, including anode pole piece, negative pole pole
Sheet, barrier film, electrolyte and shell, described anode piece of lithium ion secondary battery is by collector, positive-active
Material, conductive agent and binding agent composition, containing transition metal in described positive electrode active materials, described transition gold
Acetylene compound that metal surface has carbon number to be 2 ~ 10 by chemical bonds and derivant, carbon number
It is in the alkyl that mercaptan, sulfide, hydrogen phosphide and carbon number are 1 ~ 10 replacement phosphide of 1 ~ 10
Plant or several.
The embodiment of the present invention third aspect provide lithium ion battery be applicable to high voltage occasion, 4.5V and with
There is under upper high voltage good cycle performance, in its preparation method, can be at prepared lithium rechargeable battery
Complete " be placed in gas atmosphere and shelve ", it is also possible to anode piece of lithium ion secondary battery is being cut into slices it before
Afterwards or complete making after core is placed in housing.
Embodiment one
The preparation method of a kind of anode piece of lithium ion secondary battery, comprises the following steps:
By 800 grams of positive electrode active materials LiNi0.5Mn1.5O4, 100 grams of conductive agent acetylene black, 100 grams of binding agents
Kynoar (PVDF), joins in 800 grams of N-Methyl pyrrolidone solution (nmp solution),
De-airing mixer stirs 2h, prepares anode sizing agent；
This anode sizing agent is coated on aluminium foil uniformly, through 110 DEG C of drying, rolling, is subsequently placed at containing dry
In the atmosphere of dry acetylene gas, take out after shelving under room temperature 2 hours, prepare lithium ion secondary battery positive electrode
Pole piece.
In described anode piece of lithium ion secondary battery, the surface of transition metal Ni and Mn is coated with acetylene gas
Molecule.
The preparation of cathode pole piece of lithium ion secondary battery
By 920 grams of negative active core-shell material native graphites, 30 grams of binding agent butadiene-styrene rubber breast (SBR), 30 grams of carboxylics
Sodium carboxymethylcellulose pyce (CMC) joins in 500 grams of water, stirs 2h, prepare negative pole in de-airing mixer
Slurry, is uniformly coated to cathode size on Copper Foil, obtains lithium ion secondary electricity through 120 DEG C of drying, rolling
Pond cathode pole piece.
The preparation of electrolyte
In agitator, add 500 grams of ethylene carbonates and 500 grams of Ethyl methyl carbonate, stir 20min, generate
Mixed solvent, then 125g LiPF6 is added in the middle of solvent, continue stirring 20 minutes, obtain electrolyte.
The assembling of lithium rechargeable battery
By the anode piece of lithium ion secondary battery prepared in the present embodiment one, cathode pole piece of lithium ion secondary battery
And barrier film is successively by the battery core of up-coiler stacking wound into rolls, and the battery core obtained is put into one end open
In housing, inject the electrolyte prepared in the present embodiment one, after sealing, make lithium rechargeable battery.
Embodiment two
The present embodiment two uses the method identical with embodiment one to prepare anode piece of lithium ion secondary battery, and institute is not
Same is to be placed in the atmosphere containing the acetylene gas being dried in rolling, takes out after shelving 1 hour under room temperature,
Prepare anode piece of lithium ion secondary battery.
Prepare lithium rechargeable battery by the method identical with embodiment one, except for the difference that use the present embodiment two institute
The anode piece of lithium ion secondary battery assemble prepared, prepares lithium rechargeable battery after sealing.
Embodiment three
The present embodiment three uses the method identical with embodiment one to prepare anode piece of lithium ion secondary battery, and institute is not
Be to be placed in before the most non-rolling in the atmosphere containing dry phosphine gas, shelve 6 under room temperature
Take out after hour, press normal procedure rolling subsequently, prepare anode piece of lithium ion secondary battery.
Prepare lithium rechargeable battery by the method identical with embodiment one, except for the difference that use the present embodiment three institute
The anode piece of lithium ion secondary battery assemble prepared, prepares lithium rechargeable battery after sealing.
Embodiment four
The present embodiment four uses the method identical with embodiment one to prepare anode piece of lithium ion secondary battery, and institute is not
Same is to be placed in the atmosphere containing the hydrogen sulfide gas being dried in rolling, takes after shelving 2 hours under room temperature
Go out, prepare anode piece of lithium ion secondary battery.
Prepare lithium rechargeable battery by the method identical with embodiment one, except for the difference that use the present embodiment four institute
The anode piece of lithium ion secondary battery assemble prepared, prepares lithium rechargeable battery after sealing.
Embodiment five
The present embodiment five uses the method identical with embodiment one to prepare anode piece of lithium ion secondary battery, and institute is not
Be to be placed in before the most non-rolling containing dry hydrogen phosphide and the mixed gas (volume of hydrogen sulfide
Than be 1:1) atmosphere in, after shelving under room temperature 0.5 hour take out, press normal procedure rolling subsequently, make
Obtain anode piece of lithium ion secondary battery.
Prepare lithium rechargeable battery by the method identical with embodiment one, except for the difference that use the present embodiment five institute
The anode piece of lithium ion secondary battery assemble prepared, prepares lithium rechargeable battery after sealing.
Embodiment six
The present embodiment six uses the method identical with embodiment one to prepare anode piece of lithium ion secondary battery, and institute is not
Be the positive electrode active materials used be rich lithium solid-solution material
0.5(Li2MnO3)0.5(LiNi1/3Co1/3Mn1/3O2), other step is identical with embodiment one, prepare lithium from
Sub-anode of secondary battery pole piece.
Prepare lithium rechargeable battery by the method identical with embodiment one, except for the difference that use the present embodiment six institute
The anode piece of lithium ion secondary battery assemble prepared, prepares lithium rechargeable battery after sealing.
Embodiment seven
The present embodiment seven uses the method identical with embodiment three to prepare anode piece of lithium ion secondary battery, and institute is not
Be the positive electrode active materials used be rich lithium solid-solution material
0.7(Li2MnO3)0.3(LiNi0.4Co0.2Mn0.4O2), other step is identical with embodiment three, prepare lithium from
Sub-anode of secondary battery pole piece.
Prepare lithium rechargeable battery by the method identical with embodiment one, except for the difference that use the present embodiment seven institute
The anode piece of lithium ion secondary battery assemble prepared, prepares lithium rechargeable battery after sealing.
Embodiment eight
The present embodiment eight uses the method identical with embodiment one to prepare anode piece of lithium ion secondary battery, and institute is not
Be the positive electrode active materials used be rich lithium solid-solution material 0.4 (Li2MnO3)0.6(LiNi0.5Mn0.5O2),
And, it is pole piece to be placed in containing the acetylene being dried and the mixed gas of hydrogen sulfide before the most non-rolling
In the atmosphere of (volume ratio is 2:1), take out after shelving under room temperature 4 hours, press normal procedure rolling subsequently,
Prepare anode piece of lithium ion secondary battery.
Prepare lithium rechargeable battery by the method identical with embodiment one, except for the difference that use the present embodiment eight institute
The anode piece of lithium ion secondary battery assemble prepared, prepares lithium rechargeable battery after sealing.
Comparative example one
Comparative example one uses collector, positive electrode active materials, conductive agent all identical with embodiment one with binding agent,
Its preparation method includes: take positive electrode active materials, conductive agent, binding agent and solvent, mixes, stirs, system
Obtain anode sizing agent, anode sizing agent is coated with on a current collector, dry and rolling, do not include " being placed in gas gas
Atmosphere is shelved " step, prepare lithium rechargeable battery.
Comparative example two
Comparative example two uses the method identical with comparative example one to prepare lithium rechargeable battery, except that use
Positive electrode be rich lithium solid-solution material 0.5 (Li2MnO3)0.5(LiNi1/3Co1/3Mn1/3O2), other step with
Comparative example one is identical, does not includes the step of " be placed in gas atmosphere and shelve ", prepare lithium from
Sub-secondary cell.
Above example and comparative example prepare sample for following effect example performance test.
1. anode piece of lithium ion secondary battery surface-element is analyzed
Use x-ray photoelectron spectroscopy (XPS) to above-described embodiment one～eight, comparative example one and contrast
Anode piece of lithium ion secondary battery prepared by example two has carried out surface-element analysis, with prove really have with
The corresponding molecule of gas atmosphere covers on anode pole piece surface.Method of testing is: use PHI company of the U.S. raw
The PHI5800 type x-ray photoelectron spectroscopy produced, is furnished with Mg/Al double anode and monochromatic x-ray source, has 16
The multichannel detector of individual passage.This experiment monochromatic Al K alpha ray (h ν=1486.6eV), analysis room's vacuum
Degree is 5 × 10-8Pa, with polluting C1s(284.8eV) calibrate as electric charging effect.Test result is summarized as follows table:
Table 1. anode piece of lithium ion secondary battery surface-element analysis result
| Anode pole piece | Surface detection element |
| Embodiment one | C(acetylene carbon) |
| Embodiment two | C(acetylene carbon) |
| Embodiment three | P |
| Embodiment four | S |
| Embodiment five | P、S |
| Embodiment six | C(acetylene carbon) |
| Embodiment seven | P |
| Embodiment eight | C(acetylene carbon), S |
| Comparative example one | / |
| Comparative example two | / |
As it can be seen from table 1 the anode pole piece processed through " be placed in gas atmosphere and shelve " (embodiment one～
Eight) surface, can detect the element of corresponding gas, and without the pole piece (comparative example one of this gas treatment
With two) then fail to detect.Prove to process through " be placed in gas atmosphere and shelve ", corresponding to gas atmosphere
Molecule passed through chemical bond combined with some site on anode pole piece surface.
2. lithium rechargeable battery cycle performance test
To enter according to the lithium rechargeable battery prepared by above-described embodiment one ~ eight, comparative example one and comparative example two
Row cycle performance is tested.Method of testing is: with correct method, lithium rechargeable battery is loaded secondary cell
On ability meter BS-9300, the lithium rechargeable battery (point that embodiment one ~ five and comparative example one are prepared
Spar type positive electrode LiNi0.5Mn1.5O4) first with 1C constant-current constant-voltage charging to 4.9V, shelve 5 minutes,
It is discharged to 3.0V with 1C, then with 1C constant-current constant-voltage charging to 4.9V, circulation 100 times like this；To enforcement
(positive electrode active materials is rich lithium solid solution material to the lithium rechargeable battery that example six ~ eight and comparative example two prepare
Material)) first with 1C constant-current constant-voltage charging to 4.6V, shelve 5 minutes, be discharged to 3.0V with 1C, then with 1C
Constant-current constant-voltage charging, to 4.6V, circulates 100 times like this.After loop ends, treat lithium rechargeable battery temperature
Degree recovers room temperature, fully charged with 1C, then is discharged to 3.0V with 1C, draws residual capacity, by residual capacity
I.e. obtaining capability retention divided by circulation volume first, acquired results is as shown in table 2.
Table 2. lithium rechargeable battery cycle performance is tested
| Battery | Capacity surplus ratio (%) |
| Embodiment one | 93 |
| Embodiment two | 90 |
| Embodiment three | 95 |
| Embodiment four | 92 |
| Embodiment five | 90 |
| Embodiment six | 78 |
| Embodiment seven | 79 |
| Embodiment eight | 74 |
| Comparative example one | 67 |
| Comparative example two | 59 |
As can be seen from Table 2, the lithium rechargeable battery that the embodiment of the present invention one ~ embodiment five provides is passing through
After 100 circulations, capability retention is up to 95%, minimum 90%, and uses identical positive electrode active materials
Lithium rechargeable battery provided in comparative example one only has 67% at capability retention after 100 circulations.
The lithium rechargeable battery that the embodiment of the present invention six, seven and eight provides keeps at capacity after 100 circulations
Rate is up to 79%, minimum 74%, and is the lithium of the comparative example two using lithium-rich anode active material equally
Ion secondary battery only has 59% at capacity surplus ratio after 100 circulations, it can thus be seen that this
The lithium rechargeable battery that bright embodiment provides has good high voltage bearing performance, and cycle performance obtains simultaneously
Improve.
Claims (10)
1. an anode piece of lithium ion secondary battery, described anode piece of lithium ion secondary battery by collector,
Positive electrode active materials, conductive agent and binding agent composition, it is characterised in that contain in described positive electrode active materials
Transition metal, the acetylene compound that described transiting metal surface has carbon number to be 2～10 by chemical bonds
And mercaptan, hydrogen sulfide, hydrogen phosphide and the carbon number that derivant, carbon number are 1～10 is 1～10
Alkyl replaces one or more in phosphide.
2. a kind of anode piece of lithium ion secondary battery as claimed in claim 1, it is characterised in that described
The platform voltage of positive electrode active materials is 4.5～5V.
3. a kind of anode piece of lithium ion secondary battery as claimed in claim 1, it is characterised in that described
Positive electrode active materials is LiMxMn(2-x)O4, wherein M one in transition metal Ni, Co and Fe or
Several, 0≤x≤2, or described positive electrode active materials is xLi2MnO3(1-x)LiMO2, wherein M was selected from
Cross one or more in W metal, Co and Mn, 0≤x≤1.
4. a kind of anode piece of lithium ion secondary battery as claimed in claim 1, it is characterised in that described
Transiting metal surface has acetylene, propine, hydrogen sulfide, hydrogen phosphide, trimethyl-phosphine and three by chemical bonds
One or more in ethyl phosphine.
5. the preparation method of an anode piece of lithium ion secondary battery, it is characterised in that comprise the following steps:
Take positive electrode active materials, conductive agent, binding agent and solvent, mix, stir, prepare anode sizing agent,
The platform voltage of described positive electrode active materials is 4.5～5V, containing transition metal in described positive electrode active materials；
Being coated with on a current collector by described anode sizing agent, step subsequently also includes drying, rolling and is placed in gas
Bromhidrosis atmosphere is shelved, described gas be carbon number be acetylene compound and derivant, the carbon atom of 2～10
Number is in the alkyl that mercaptan, hydrogen sulfide, hydrogen phosphide and carbon number the are 1～10 replacement phosphide of 1～10
One or more, described drying, rolling and be placed in the order shelved in gas atmosphere and do not limit, prepare lithium ion
Secondary anode pole piece.
The preparation method of a kind of anode piece of lithium ion secondary battery the most as claimed in claim 5, its feature
Being, the platform voltage of described positive electrode active materials is 4.5～5V.
The preparation method of a kind of anode piece of lithium ion secondary battery the most as claimed in claim 5, its feature
Being, described positive electrode active materials is LiMxMn(2-x)O4, wherein M is selected from transition metal Ni, Co and Fe
In one or more, 0≤x≤2, or described positive electrode active materials is xLi2MnO3(1-x)LiMO2, wherein
One or more in transition metal Ni, Co and Mn of M, 0≤x≤1.
The preparation method of a kind of anode piece of lithium ion secondary battery the most as claimed in claim 5, its feature
Being, described gas is in acetylene, propine, hydrogen sulfide, hydrogen phosphide, trimethyl-phosphine and triethyl phosphine
Plant or several.
The preparation method of a kind of anode piece of lithium ion secondary battery the most as claimed in claim 5, its feature
Be, described in be placed in the time shelved in gas atmosphere be 0.1～24 hour.
10. a lithium ion battery, including anode pole piece, cathode pole piece, barrier film, electrolyte and shell, its
Be characterised by, described anode piece of lithium ion secondary battery by collector, positive electrode active materials, conductive agent and
Binding agent forms, and containing transition metal in described positive electrode active materials, described transiting metal surface is by chemistry
Key is combined with acetylene compound that carbon number is 2～10 and derivant thereof, carbon number is 1～10 mercaptan,
Hydrogen sulfide, hydrogen phosphide and carbon number are one or more in the alkyl replacement phosphide of 1～10.
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| CN1732581A (en) * | 2002-10-31 | 2006-02-08 | 三菱化学株式会社 | Additive for positive electrode material for lithium secondary battery, positive electrode material for lithium secondary battery, and positive electrode and lithium secondary battery using the positi |
| CN1965428A (en) * | 2004-08-26 | 2007-05-16 | 松下电器产业株式会社 | Composite particle for electrode, its manufacturing method, and nonaqueous electrolyte secondary battery |
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| CN1732581A (en) * | 2002-10-31 | 2006-02-08 | 三菱化学株式会社 | Additive for positive electrode material for lithium secondary battery, positive electrode material for lithium secondary battery, and positive electrode and lithium secondary battery using the positi |
| CN101015074A (en) * | 2004-08-18 | 2007-08-08 | 财团法人电力中央研究所 | Organic electrolyte battery, and process for producing positive electrode sheet for use therein |
| CN1965428A (en) * | 2004-08-26 | 2007-05-16 | 松下电器产业株式会社 | Composite particle for electrode, its manufacturing method, and nonaqueous electrolyte secondary battery |
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