CN102800890A - Lithium-ion battery and preparation method for same - Google Patents
Lithium-ion battery and preparation method for same Download PDFInfo
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- CN102800890A CN102800890A CN2011101407454A CN201110140745A CN102800890A CN 102800890 A CN102800890 A CN 102800890A CN 2011101407454 A CN2011101407454 A CN 2011101407454A CN 201110140745 A CN201110140745 A CN 201110140745A CN 102800890 A CN102800890 A CN 102800890A
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- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention provides a lithium-ion battery, comprising a positive pole, a negative pole and an electrolyte. The lithium-ion battery is characterized in that the negative pole is made of Si alloy; and the electrolyte comprises lithium hexafluorophosphate, ethylene carbonate, dimethyl carbonate, fluoroethylene carbonate and diethyl carbonate. In the lithium-ion battery, a layer of compact and flexible solid electrolyte interface film can be formed on the surface of the negative pole which is made of the Si alloy during pre-flushing, thus effectively suppressing the own expansion of the Si alloy material, and improving the cycle performance of the battery. The invention further provides a preparation method for the lithium-ion battery.
Description
[technical field]
The present invention relates to the secondary cell field, relate in particular to a kind of lithium ion battery and preparation method thereof.
[background technology]
At present, lithium ion battery has been widely used on various digital devices and the various electrical equipment, and the performance index of weighing lithium ion on the market comprise the size of capacity and the height of cycle performance etc.Cycle performance is meant repeatedly charge and discharge cycles capability retention afterwards of battery.
The development key of lithium ion battery is the development of electrode material.Traditional lithium ion battery negative material all is carbon materials basically, like electrographite, native graphite, carbonaceous mesophase spherules, petroleum coke, carbon fiber, pyrolysis resin carbon etc.The Si alloy material with respect to traditional carbon materials, has higher energy density as the new type lithium ion battery negative material.Yet the Si alloy material can be because the expansion of self causes the decline of cycle performance of battery as lithium ion battery negative.
[summary of the invention]
Based on this, be necessary to provide a kind of cycle performance lithium ion battery and preparation method thereof preferably.
A kind of lithium ion battery comprises: positive pole, negative pole and electrolyte; Said negative pole material is the Si alloy, and said electrolyte comprises: lithium hexafluoro phosphate, ethylene carbonate, dimethyl carbonate, fluorinated ethylene carbonate and diethyl carbonate.
Preferably, the quality proportioning of said electrolyte is: 10～20 parts lithium hexafluoro phosphate, 20～30 parts ethylene carbonate, 10～20 parts dimethyl carbonate, 15～25 parts fluorinated ethylene carbonate and 20～30 parts diethyl carbonate.
Preferably, the quality proportioning of said electrolyte is: 13～15 parts lithium hexafluoro phosphate, 25～27 parts ethylene carbonate, 15～17 parts dimethyl carbonate, 18～20 parts fluorinated ethylene carbonate and 25～27 parts diethyl carbonate.
Preferably, said Si alloy is SiC.
A kind of preparation method of lithium ion battery comprises the steps:
Step 1, preparing electrolyte; Said electrolyte comprises: lithium hexafluoro phosphate, ethylene carbonate, dimethyl carbonate, fluorinated ethylene carbonate and diethyl carbonate;
Step 2, selection material are the negative pole and the electric core of anodal making of Si alloy, and said electrolyte is injected said electric core;
Step 3, dash in advance after said electric core sealed, obtain said lithium ion battery.
Preferably, in the step 1, the quality proportioning of said electrolyte is: 10～20 parts lithium hexafluoro phosphate, 20～30 parts ethylene carbonate, 10～20 parts dimethyl carbonate, 15～25 parts fluorinated ethylene carbonate and 20～30 parts diethyl carbonate.
Preferably, the quality proportioning of said electrolyte is: 13～15 parts lithium hexafluoro phosphate, 25～27 parts ethylene carbonate, 15～17 parts dimethyl carbonate, 18～20 parts fluorinated ethylene carbonate and 25～27 parts diethyl carbonate.
Preferably, in the step 2, said Si alloy is SiC.
Preferably, step 3 also comprise said electric core sealed after, in advance towards preceding ageing operation.
Preferably, step 3 also comprises the operation of dashing the back high temperature ageing in advance.
This lithium ion battery, in advance towards the time can form the solid electrolyte interface film that one deck is fine and close and have toughness in the negative terminal surface of Si alloy material, thereby effectively suppress the expansion of Si alloy material self, improved the cycle performance of battery.
[description of drawings]
Fig. 1 is preparation method's the flow chart of the lithium ion battery of an execution mode;
The lithium ion battery that Fig. 2 makes for embodiment 1 carries out the outside drawing after the 25 degree circulations;
The lithium ion battery that Fig. 3 makes for Comparative Examples 1 carries out the outside drawing after the 25 degree circulations;
Fig. 4 carries out the cycle graph that 25 degree circulate for embodiment 1 with the lithium ion battery that Comparative Examples 1 makes;
The lithium ion battery that Fig. 5 makes for embodiment 2 carries out the outside drawing after the 25 degree circulations;
The lithium ion battery that Fig. 6 makes for Comparative Examples 2 carries out the outside drawing after the 25 degree circulations;
Fig. 7 carries out the cycle graph that 25 degree circulate for embodiment 2 with the lithium ion battery that Comparative Examples 2 makes;
The lithium ion battery that Fig. 8 makes for embodiment 3 carries out the outside drawing after the 25 degree circulations;
The lithium ion battery that Fig. 9 makes for Comparative Examples 3 carries out the outside drawing after the 25 degree circulations;
Figure 10 carries out the cycle graph that 25 degree circulate for embodiment 3 with the lithium ion battery that Comparative Examples 3 makes.
[embodiment]
Below in conjunction with accompanying drawing and embodiment lithium ion battery and preparation method thereof is done further description.
The lithium ion battery of one execution mode comprises: positive pole, negative pole and electrolyte.
Anodal material is positive electrode commonly used, and general can be nickel manganese cobalt acid lithium (NMC), cobalt acid lithium (LCO), nickel cobalt lithium aluminate (NCA) etc.
The negative pole material is the Si alloy.
General, the negative pole material can be the direct compound SiC that obtains of Si and C, also can be that Si elder generation and transition metal are compound, again with the compound SiC that obtains of C.
Electrolyte comprises: lithium hexafluoro phosphate (LiPF
6), ethylene carbonate (EC), dimethyl carbonate (DMC), fluorinated ethylene carbonate (FEC) and diethyl carbonate (DEC).
LiPF
6Be electrolyte, lithium ion is provided.EC, DMC and DEC are solvent, and EC plays the effect of dissolving LiPF6, and DMC, DEC play the effect that reduces the electrolyte viscosity, improves conductance.(Solid electrolyte interface, SEI) film is helpful, makes the SEI film that forms have toughness, is not easy to be destroyed to forming solid electrolyte interface for FEC.
Physicochemical properties such as the chemical composition of SEI film, structure, texture and stability are the keys of decision lithium ion battery negative/electrolyte compatibility, optimize SEI film character.When electric core initial charge; Under certain current potential; Film forming agent in lithium ion, the electrolyte is in negative terminal surface generation reduction reaction; The chemical substance of decomposing deposits the formation layer protecting film in negative terminal surface, prevents solvent and negative reaction, and the formed film of different film for additive has various structure and effect.Through adding FEC, comprise stability compound such as LiF, SiF preferably in the feasible SEI film that forms, thereby make that the SEI film toughness that forms is better.Formed film also comprises Si-OCH
2CH
2OCO
2Li ,-Si-CH
2CH
2OCO
2Li, R (OCO
2Li)
2Deng compound.
In a preferred embodiment, the quality proportioning of electrolyte is: 10～20 parts lithium hexafluoro phosphate, 20～30 parts ethylene carbonate, 10～20 parts dimethyl carbonate, 15～25 parts fluorinated ethylene carbonate and 20～30 parts diethyl carbonate.
Preferred especially, the quality proportioning of electrolyte is: 13～15 parts lithium hexafluoro phosphate, 25～27 parts ethylene carbonate, 15～17 parts dimethyl carbonate, 18～20 parts fluorinated ethylene carbonate and 25～27 parts diethyl carbonate.
This lithium ion battery, in advance towards the time can form the SEI film that one deck is fine and close and have toughness in the negative terminal surface of Si alloy material, thereby effectively suppress the expansion of Si alloy material self, improved the cycle performance of battery.
The preparation method of the lithium ion battery of an execution mode as shown in Figure 1 comprises the steps:
S10, preparing electrolyte.
Electrolyte comprises: lithium hexafluoro phosphate, ethylene carbonate, dimethyl carbonate, fluorinated ethylene carbonate and diethyl carbonate.
Preferably, the quality proportioning of electrolyte is: 10～20 parts lithium hexafluoro phosphate, 20～30 parts ethylene carbonate, 10～20 parts dimethyl carbonate, 15～25 parts fluorinated ethylene carbonate and 20～30 parts diethyl carbonate.
Preferred especially, the quality proportioning of electrolyte is: 13～15 parts lithium hexafluoro phosphate, 25～27 parts ethylene carbonate, 15～17 parts dimethyl carbonate, 18～20 parts fluorinated ethylene carbonate and 25～27 parts diethyl carbonate.
S20, selection material are the negative pole and the electric core of anodal making of Si alloy, and inject the electrolyte into electric core.
Adopt the positive pole of unlike material, and the negative pole of the Si alloy material that provides of different manufacturers, make 18650 types electricity core, inject the electrolyte into.
General, the negative pole material can be the direct compound SiC that obtains of Si and C, also can be that Si elder generation and transition metal are compound, again with the compound SiC that obtains of C.
S30, electric core sealed carry out ageing, dash and high temperature ageing in advance, obtain lithium ion battery.
Be the specific embodiment part below.
Embodiment 1
1, configuration electrolyte.
Electrolyte prescription is:
2, adopt the positive pole of nickel manganese cobalt acid lithium (NMC) material, the negative pole of SiC material is made 18650 types electricity core, injects the electrolyte into.
3, electric core seals and carries out ageing, preliminary filling, and high temperature ageing obtains lithium ion battery.
Comparative Examples 1
1, configuration electrolyte.
Electrolyte prescription is:
2, adopt the positive pole of nickel manganese cobalt acid lithium (NMC) material, the negative pole of SiC material is made 18650 types electricity core, injects the electrolyte into.
3, electric core seals and carries out ageing, preliminary filling, and high temperature ageing obtains lithium ion battery.
Embodiment 1 is carried out 25 degree circulations with the lithium ion battery that Comparative Examples 1 makes, and endless form is+0.5C/-0.5C, by condition: voltage: 3.0V～4.2V, electric current: 0.02C.
The lithium ion battery that Fig. 2 makes for embodiment 1 carries out the outside drawing after the 25 degree circulations, and the lithium ion battery that Fig. 3 makes for Comparative Examples 1 carries out the outside drawing after the 25 degree circulations.
Can find out that by Fig. 2 and Fig. 3 the electric core CID of the lithium ion battery that embodiment 1 makes is upset not, the electric core CID upset of the lithium ion battery that Comparative Examples 1 makes.
The cycle graph that the lithium ion battery that Fig. 4 makes for embodiment 1 and Comparative Examples 1 carries out 25 degree circulations, the cycle graph of the lithium ion battery that the A curve makes for embodiment 1 among the figure, the B curve is the cycle graph of the lithium ion battery that makes of Comparative Examples 1 among the figure.
Pole piece thickness before negative plate thickness direction expansion rate TP=(pole piece thickness before circulation back pole piece thickness-circulation)/circulation; Pole piece thickness before the expansion rate WP=of Width (pole piece thickness before circulation back pole piece width-circulation)/circulation.
Whether electric core circulation conservation rate, the CID that contrast is marked with two kinds of electrolyte overturns, TP, WP, if the circulation conservation rate is high, CID does not have upset, TP is low, WP is low, explain that electrolyte can better improve expansion and circulates.
Can find out by Fig. 4; The lithium ion battery that embodiment 1 makes is higher than the electric core circulation conservation rate of the lithium ion battery that Comparative Examples 1 makes; The electric core negative plate thickness direction expansion rate TP=40.7% of the lithium ion battery that embodiment 1 makes; The electric core negative plate thickness direction expansion rate TP=45.7% of the lithium ion battery that Comparative Examples 1 makes; The negative plate Width expansion rate WP=3.7% of the lithium ion battery that embodiment 1 makes, the negative plate Width expansion rate WP=4.5% of the lithium ion battery that Comparative Examples 1 makes.
Therefore, the electrolyte of the use of the lithium ion battery among the embodiment 1 can better improve expansion and circulation.
Embodiment 2
1, configuration electrolyte.
Electrolyte prescription is:
2, adopt the positive pole of cobalt acid lithium (LCO) material, the negative pole of SiC material is made 18650 types electricity core, and electrolyte injects.
3, electric core seals and carries out ageing, preliminary filling, high temperature ageing.
Comparative Examples 2
1, configuration electrolyte.
Electrolyte prescription is:
2, adopt the positive pole of cobalt acid lithium (LCO) material, the negative pole of SiC material is made 18650 types electricity core, and electrolyte injects.
3, electric core seals and carries out ageing, preliminary filling, high temperature ageing.
Embodiment 2 is carried out 25 degree circulations with the lithium ion battery that Comparative Examples 2 makes, and endless form is+0.5C/-0.5C, by condition: voltage: 3.0V～4.2V, electric current: 0.02C.
The lithium ion battery that Fig. 5 makes for embodiment 2 carries out the outside drawing after the 25 degree circulations, and the lithium ion battery that Fig. 6 makes for Comparative Examples 2 carries out the outside drawing after the 25 degree circulations.
Can find out that by Fig. 5 and Fig. 6 the electric core CID of the lithium ion battery that embodiment 2 makes is upset not, the electric core CID upset of the lithium ion battery that Comparative Examples 2 makes.
The cycle graph that the lithium ion battery that Fig. 7 makes for embodiment 2 and Comparative Examples 2 carries out 25 degree circulations, the cycle graph of the lithium ion battery that the A curve makes for embodiment 2 among the figure, the B curve is the cycle graph of the lithium ion battery that makes of Comparative Examples 2 among the figure.
Pole piece thickness before negative plate thickness direction expansion rate TP=(pole piece thickness before circulation back pole piece thickness-circulation)/circulation; Pole piece thickness before the expansion rate WP=of Width (pole piece thickness before circulation back pole piece width-circulation)/circulation.
Whether electric core circulation conservation rate, the CID that contrast is marked with two kinds of electrolyte overturns, TP, WP, if the circulation conservation rate is high, CID does not have upset, TP is low, WP is low, explain that electrolyte can better improve expansion and circulates.
Can find out by Fig. 7; The lithium ion battery that embodiment 2 makes is higher than the electric core circulation conservation rate of the lithium ion battery that Comparative Examples 2 makes; The electric core negative plate thickness direction expansion rate TP=41.7% of the lithium ion battery that embodiment 2 makes; The electric core negative plate thickness direction expansion rate TP=46.7% of the lithium ion battery that Comparative Examples 2 makes; The negative plate Width expansion rate WP=3.5% of the lithium ion battery that embodiment 2 makes, the negative plate Width expansion rate WP=4.7% of the lithium ion battery that Comparative Examples 2 makes.
Therefore, the electrolyte of the use of the lithium ion battery among the embodiment 2 can better improve expansion and circulation.
Embodiment 3
1, configuration electrolyte.
Electrolyte prescription is:
2, adopt the positive pole of nickel cobalt lithium aluminate (NCA) material, the negative pole of SiC material is made 18650 types electricity core, and electrolyte injects.
3, electric core seals and carries out ageing, preliminary filling, high temperature ageing.
Comparative Examples 3
1, configuration electrolyte.
Electrolyte prescription is:
2, adopt the positive pole of nickel cobalt lithium aluminate (NCA) material, the negative pole of SiC material is made 18650 types electricity core, and electrolyte injects.
3, electric core seals and carries out ageing, preliminary filling, high temperature ageing.
Embodiment 3 is carried out 25 degree circulations with the lithium ion battery that Comparative Examples 3 makes, and endless form is+0.5C/-0.5C, by condition: voltage: 3.0V～4.2V, electric current: 0.02C.
The lithium ion battery that Fig. 8 makes for embodiment 3 carries out the outside drawing after the 25 degree circulations, and the lithium ion battery that Fig. 9 makes for Comparative Examples 3 carries out the outside drawing after the 25 degree circulations.
Can find out that by Fig. 8 and Fig. 9 the electric core CID of the lithium ion battery that embodiment 3 makes is upset not, the electric core CID upset of the lithium ion battery that Comparative Examples 3 makes.
The cycle graph that the lithium ion battery that Figure 10 makes for embodiment 3 and Comparative Examples 3 carries out 25 degree circulations, the cycle graph of the lithium ion battery that the A curve makes for embodiment 3 among the figure, the B curve is the cycle graph of the lithium ion battery that makes of Comparative Examples 3 among the figure.
Pole piece thickness before negative plate thickness direction expansion rate TP=(pole piece thickness before circulation back pole piece thickness-circulation)/circulation; Pole piece thickness before the expansion rate WP=of Width (pole piece thickness before circulation back pole piece width-circulation)/circulation.
Whether electric core circulation conservation rate, the CID that contrast is marked with two kinds of electrolyte overturns, TP, WP, if the circulation conservation rate is high, CID does not have upset, TP is low, WP is low, explain that electrolyte can better improve expansion and circulates.
Can find out by Figure 10; The lithium ion battery that embodiment 3 makes is higher than the electric core circulation conservation rate in lithium-ion electric 7 ponds that Comparative Examples 3 makes; The electric core negative plate thickness direction expansion rate TP=42.7% of the lithium ion battery that embodiment 3 makes; The electric core negative plate thickness direction expansion rate TP=47.7% of the lithium ion battery that Comparative Examples 3 makes; The negative plate Width expansion rate WP=3.8% of the lithium ion battery that embodiment 3 makes, the negative plate Width expansion rate WP=4.5% of the lithium ion battery that Comparative Examples 3 makes.
Therefore, the electrolyte of the use of the lithium ion battery among the embodiment 3 can better improve expansion and circulation.
Embodiment 4
1, configuration electrolyte.
Electrolyte prescription is:
2, adopt the positive pole of nickel manganese cobalt acid lithium (NMC) material, the negative pole of SiC material is made 18650 types electricity core, injects the electrolyte into.
3, electric core seals and carries out ageing, preliminary filling, and high temperature ageing obtains lithium ion battery.
Embodiment 5
1, configuration electrolyte.
Electrolyte prescription is:
2, adopt the positive pole of cobalt acid lithium (LCO) material, the negative pole of SiC material is made 18650 types electricity core, injects the electrolyte into.
3, electric core seals and carries out ageing, preliminary filling, and high temperature ageing obtains lithium ion battery.
Embodiment 6
1, configuration electrolyte.
Electrolyte prescription is:
2, adopt the positive pole of nickel cobalt lithium aluminate (NCA) material, the negative pole of SiC material is made 18650 types electricity core, injects the electrolyte into.
3, electric core seals and carries out ageing, preliminary filling, and high temperature ageing obtains lithium ion battery.
The above embodiment has only expressed one or more execution modes of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art under the prerequisite that does not break away from the present invention's design, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with accompanying claims.
Claims (10)
1. a lithium ion battery comprises: positive pole, negative pole and electrolyte; It is characterized in that said negative pole material is the Si alloy, said electrolyte comprises: lithium hexafluoro phosphate, ethylene carbonate, dimethyl carbonate, fluorinated ethylene carbonate and diethyl carbonate.
2. lithium ion battery as claimed in claim 1; It is characterized in that the quality proportioning of said electrolyte is: 10～20 parts lithium hexafluoro phosphate, 20～30 parts ethylene carbonate, 10～20 parts dimethyl carbonate, 15～25 parts fluorinated ethylene carbonate and 20～30 parts diethyl carbonate.
3. lithium ion battery as claimed in claim 2; It is characterized in that the quality proportioning of said electrolyte is: 13～15 parts lithium hexafluoro phosphate, 25～27 parts ethylene carbonate, 15～17 parts dimethyl carbonate, 18～20 parts fluorinated ethylene carbonate and 25～27 parts diethyl carbonate.
4. lithium ion battery as claimed in claim 1 is characterized in that, said Si alloy is SiC.
5. the preparation method of a lithium ion battery is characterized in that, comprises the steps:
Step 1, preparing electrolyte; Said electrolyte comprises: lithium hexafluoro phosphate, ethylene carbonate, dimethyl carbonate, fluorinated ethylene carbonate and diethyl carbonate;
Step 2, selection material are the negative pole and the electric core of anodal making of Si alloy, and said electrolyte is injected said electric core;
Step 3, dash in advance after said electric core sealed, obtain said lithium ion battery.
6. the preparation method of lithium ion battery as claimed in claim 5; It is characterized in that; In the step 1, the quality proportioning of said electrolyte is: 10～20 parts lithium hexafluoro phosphate, 20～30 parts ethylene carbonate, 10～20 parts dimethyl carbonate, 15～25 parts fluorinated ethylene carbonate and 20～30 parts diethyl carbonate.
7. the preparation method of lithium ion battery as claimed in claim 6; It is characterized in that the quality proportioning of said electrolyte is: 13～15 parts lithium hexafluoro phosphate, 25～27 parts ethylene carbonate, 15～17 parts dimethyl carbonate, 18～20 parts fluorinated ethylene carbonate and 25～27 parts diethyl carbonate.
8. the preparation method of lithium ion battery as claimed in claim 5 is characterized in that, in the step 2, said Si alloy is SiC.
9. the preparation method of lithium ion battery as claimed in claim 5 is characterized in that, step 3 also comprise said electric core sealed after, in advance towards preceding ageing operation.
10. the preparation method of lithium ion battery as claimed in claim 5 is characterized in that, step 3 also comprises the operation of dashing the back high temperature ageing in advance.
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| CN2011101407454A CN102800890A (en) | 2011-05-27 | 2011-05-27 | Lithium-ion battery and preparation method for same |
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|---|---|---|---|
| CN2011101407454A CN102800890A (en) | 2011-05-27 | 2011-05-27 | Lithium-ion battery and preparation method for same |
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Cited By (1)
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Application publication date: 20121128 |