CN106169559A - A kind of cathode size, the preparation method of cathode size and use the negative plate and lithium ion battery that this cathode size makes - Google Patents
A kind of cathode size, the preparation method of cathode size and use the negative plate and lithium ion battery that this cathode size makes Download PDFInfo
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- CN106169559A CN106169559A CN201610616819.XA CN201610616819A CN106169559A CN 106169559 A CN106169559 A CN 106169559A CN 201610616819 A CN201610616819 A CN 201610616819A CN 106169559 A CN106169559 A CN 106169559A
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- 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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Abstract
The invention discloses a kind of cathode size, the preparation method of cathode size and the negative plate using this cathode size to make and lithium ion battery, component including following weight proportion: hard carbon and graphite compound 91 95%, conductive black 1 3%, Kynoar 4 6%, separately adds the oxalic acid of the total counterweight of above-mentioned material 0.1 0.3%.The lithium ion battery that the present invention uses the cathode size of technique scheme to prepare have following technical effect that battery can 10C 30C high-multiplying power discharge, and 20C/1C discharge capacity can reach 95%, and 30C/1C discharge capacity can reach more than 90%；Battery can multiplying power quick charge greatly, after 5C quick charge, 10C and 20C high-multiplying power discharge capacity release rate all up to more than 98%.
Description
Technical field
The present invention relates to a kind of lithium ion battery and preparing technical field, particularly relate to a kind of cathode size, cathode size
Preparation method and use the negative plate and lithium ion battery that this cathode size makes.
Background technology
Lithium ion battery is because being capable of repeatedly discharge and recharge, can realize big multiplying power discharging, memoryless effect by environment to external world
, many particular advantages such as the energy should be saved and utilized by people, replace conventional batteries to recycle, not environmentally, waste
The series of problems such as the energy.But battery polarization is serious when lithium battery generally exists lithium ion battery high current charge-discharge at present,
Multiplying power discharging property is poor, low temperature environment discharge capacity is few, service life short wait series of problems.This is because with conventional graphite
The best for the embedding and removing performance of carbon in the lithium battery of negative material, make metallic lithium surface in charging process uneven, cause
" Li dendrite ".So finding novel negative material, the defect improving conventional graphite negative material becomes grinding of lithium ion battery
Study carefully focus.
Hard carbon material is owing to having interlaced layer structure, and lithium ion has more more than conventional graphite in hard carbon
Embed and abjection passage, therefore there is charge/discharge rates more higher than graphite and more excellent cryogenic property, the most a large amount of micropores
Existence, also make hard carbon have more higher reversible specific capacity than graphite, be the negative material of a kind of potentiality as rich as Croesus.So
And, just because of having a large amount of staggered layer structure and lithium ion deintercalation passage so that the first charge-discharge of hard carbon material is not
Reversible capacity is greatly increased, and main cause is that substantial amounts of lithium reacts, with electrolyte, the solid electrolyte SEI generated at material surface
Caused by film.Therefore, improve the defect that hard carbon cathode material first charge-discharge efficiency is low, become an exploitation of hard carbon cathode material
Focus.
Summary of the invention
The technical problem to be solved in the present invention is for problem above, it is provided that a kind of cathode size and the preparation of cathode size
Method, the lithium ion battery using the cathode size of the present invention to prepare is capable of ultra-high magnifications discharge and recharge, and under low temperature environment
Discharge capacity performance is good, and charge-discharge velocity and capacity density are high, and negative material first charge-discharge efficiency is high, has high cycle life；
Present invention also offers a kind of negative plate using above-mentioned cathode size；
It addition, present invention also offers a kind of lithium ion battery utilizing above-mentioned negative plate.
In order to solve the problems referred to above, the present invention by the following technical solutions: a kind of cathode size, it is characterised in that: described
Cathode size includes the component of following weight proportion: hard carbon and graphite compound 91-95%, conductive black 1-3%, Kynoar
4-6%, separately adds the oxalic acid of total counterweight 0.1-0.3% of above-mentioned material.
The following is further improvement of the present invention:
In described hard carbon and graphite compound, hard carbon accounts for compound gross weight than for 10-18%.
Improve further:
Described hard carbon is micron particles, and its specific surface is 3-5m2/g。
Improve further:
Described cathode size includes the component of following weight proportion: hard carbon and graphite compound 94%, conductive black 1.5%, poly-partially
Fluorothene 4.5%, separately adds the oxalic acid of the total counterweight of above-mentioned material 0.2%.
Improve further:
The preparation method of a kind of cathode size, comprises the steps:
1), vacuum drying step, take the hard carbon of above-mentioned weight proportion and graphite compound, conductive black, Kynoar and front
State the oxalic acid of material gross weight 0.2%, as the raw material of cathode size, vacuum drying；
2), colloidal sol step, take N-Methyl pyrrolidone equiponderant with above-mentioned raw materials as solvent, by 1) in polyvinylidene fluoride
Alkene is dissolved in wherein, high-speed stirred；
3), to step 2) in preparation glue in add conductive black, stirring at low speed, obtain compound；
4) compound, in step 3) is initially charged hard carbon, stirring at low speed, obtains compound；
5) compound, in step 4) adds graphite, stirring at low speed, obtains compound；
6) compound, in step 5) adds oxalic acid, stirring at low speed, obtains compound；
7) the compound vacuum pressurize, by step 5) obtained, prepares cathode size.
Improve further:
Step 2) in sol-process, first not open cycle water, when temperature reaches 50 DEG C, then opens recirculated water, when having stirred,
Glue is without substantially caking；Mixing time is 3～4h.
Improve further:
In step 3)-step 5), mixing time is 1 h.
Improve further:
In step 5), vacuum is-0.09Mpa, and the dwell time is 1h.
A kind of negative plate, described negative plate includes negative current collector, and in the upper and lower surface of negative current collector, even spread has
Cathode size, the one side surface density of cathode size coating is 5.41-6.41mg/cm2。
A kind of lithium ion battery, including positive plate, negative plate, barrier film and aluminum-plastic composite membrane, wherein positive plate and negative plate
Alternately arranged, and barrier film is between positive plate and negative plate, aluminum-plastic composite membrane wraps positive plate, negative plate and barrier film, just
Cathode pole piece lug all uses full lug to design.
The lithium ion battery that the present invention uses the cathode size of technique scheme to prepare has following technical effect that
1, battery can 10C-30C high-multiplying power discharge, and 20C/1C discharge capacity can reach 95%, 30C/1C discharge capacity up to
To more than 90%；
2, battery can multiplying power quick charge greatly, after 5C quick charge, 10C and 20C high-multiplying power discharge capacity release rate all up to 98%
Above；
3, battery can-20 DEG C-40 DEG C electric discharges ,-20 DEG C of discharge capacities up to more than the 90% of room temperature discharge capacity, and
-40 DEG C of discharge capacities up to the 81% of rated capacity；
4, battery 10C fills 10C electric discharge persistent loop 200 weeks, and capability retention reaches more than 92%；
5, negative material first charge-discharge efficiency is up to more than 87%；
6, stable performance, can ultra-high magnifications discharge and recharge, resistance to low temperature is good, can be applicable to automobile start and stop field of power supplies, has
It is widely applied prospect.
Accompanying drawing explanation
Accompanying drawing 1 is the structural representation of battery core pole piece；
The structural representation of accompanying drawing 2 soft-package battery；
Accompanying drawing 3 is the structural representation of aluminum-shell battery；
Accompanying drawing 4 is schemed for cathode pole piece SEM；
Accompanying drawing 5 is 1C charging different multiplying discharge curve comparison diagram；
Accompanying drawing 6 is 5C charging different multiplying discharge curve comparison diagram；
Accompanying drawing 7 is 1C discharge curve comparison diagram under different temperatures.
Accompanying drawing 8 is 10C charge and discharge cycles curve chart.
Detailed description of the invention
Embodiment 1, a kind of cathode size, including solid material and liquid material, described solid material includes following weight
The component of proportioning: hard carbon and graphite compound 94%, conductive black 1.5%, Kynoar 4.5%, the another total counterweight of reinforcing body material
The oxalic acid of 0.1-0.3%, preferably 0.2%.
Described liquid material is organic solvent, preferably N-Methyl pyrrolidone.
The solid content of described cathode size is the proportion that 50%(i.e. solid material accounts for total slurry).
In described hard carbon and graphite compound, hard carbon accounts for compound gross weight ratio is 15%.
Described hard carbon is micron particles, and its specific surface is 3-5m2/g。
The preparation method of a kind of cathode size, comprises the steps:
1) hard carbon that weight proportion is 94% and graphite compound, the conductive black of 1.5%, the Kynoar of 4.5% and front, are taken
State the oxalic acid of material gross weight 0.2%, as the raw material of cathode size, vacuum drying, remove moisture removal；
2), N-Methyl pyrrolidone equiponderant with above-mentioned raw materials is taken as solvent, by molten for the Kynoar in step 1)
In wherein, use double-planet stirring (high-speed stirred) 3～4h；
In sol-process, first not open cycle water, when temperature reaches 50 DEG C, then opens recirculated water, and when having stirred, glue is without bright
Aobvious caking；
3), to step 2) in preparation glue in add conductive black, stirring at low speed 1h, obtain compound；
4) compound, in step 3) is initially charged hard carbon, stirring at low speed 1h；
Add graphite, stirring at low speed 1h；
It is eventually adding oxalic acid, stirring at low speed 1h；
Last below vacuum-0.09Mpa pressurize 1h, obtains cathode size.
A kind of negative plate, including negative current collector and above-mentioned cathode size, negative current collector covers for having conductive coating
Collector, coating layer thickness is 1-2um.
Cathode size is uniformly coated in the upper and lower surface of negative current collector, and slurry one side face on negative current collector is close
Degree is 5.85mg/cm2。
A kind of lithium ion battery, as Figure 1-3, including positive plate, negative plate, barrier film and aluminum-plastic composite membrane (or aluminum
Shell), wherein positive plate and negative plate are alternately arranged, and barrier film is between positive plate and negative plate, aluminum-plastic composite membrane (or aluminum
Shell) wrap positive plate, negative plate and barrier film, positive pole ear and negative lug and all use full lug to design.
The present embodiment prepares negative plate by above-mentioned steps, makes square battery core by the way of lamination (or winding)
Body, the battery core body being fabricated by again through encapsulation, be dried and the operation such as fluid injection, chemical conversion and partial volume and be manufactured into square battery.
Cathode size in the present invention uses hard carbon collocation graphite as active material.Owing to hard carbon material is unordered random layer
Structure, has compared with graphite material more lithium ion transmission channels, and therefore its charge-discharge velocity and capacity density are higher.By firmly
Rate charge-discharge that carbon is good and cryogenic property, it is achieved that the 30C ultra-high magnifications heavy-current discharge performance of battery and can quickly filling
The performance of full electricity, improves the defect of graphite cathode low temperature performance difference.
But hard carbon material is the most inefficient, specific surface is the biggest, and loss in efficiency is the most serious first.Therefore, the present invention adopts
Hard carbon specific surface be 3-5m2/g.Arrange in pairs or groups graphite material so that efficiency is up to more than 87% first, improves and imitates first simultaneously
The problem that rate is low.It is 10%-18% that the hard carbon selected accounts for gross weight ratio, has taken into account battery efficiency first, and composite wood simultaneously
The electronic conductivity of material and ion mobility, it is ensured that it most preferably conducts electricity embedding lithium performance.
Embodiment 2-5, as different from Example 1 cathode size proportioning parameter, table 1 is embodiment 1-5 in the present invention
Cathode size proportioning parameter list, the preparation method of the most each embodiment is the most same as in Example 1, so place no longer carries out the most detailed
Stating, design parameter value see table:
Table 1 each embodiment cathode blending ratio
| Parameter name | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Graphite/hard carbon compound (%)；(hard carbon accounting, %) | 94(15) | 92.5(12) | 91(10) | 93(16) | 95(18) |
| Conductive black (%) | 1.5 | 2 | 3 | 2 | 1 |
| Kynoar (%) | 4.5 | 5.5 | 6 | 5 | 4 |
| Solid content (%) | 50 | 52 | 49 | 50 | 48 |
| Surface density (mg/cm3) | 5.85 | 6.23 | 6.41 | 5.87 | 5.41 |
The lithium ion battery that the component of the employing present invention and preparation method are prepared from has ultra-high magnifications electric discharge with low temperature resistant
Performance.
Through test, embodiment 1 is optimum embodiment, and in embodiment 1 as a example by the lithium ion battery of preparation, its performance sees
Fig. 4-8.
As shown in Figure 4, the hard carbon in negative material is dispersed in graphite.
As shown in Figure 5, this battery can 20C-30C high-multiplying power discharge, 20C/1C discharge capacity is up to 95%, and 30C/1C
Discharge capacity ratio reaches more than 90%.
It will be appreciated from fig. 6 that 10C and 20C high-multiplying power discharge capacity release rate all up to more than 98% after 5C quick charge.
As shown in Figure 7 ,-20 DEG C of 1C discharge capacities of low temperature, up to the 92.5% of room temperature discharge capacity, still can release 81% for-40 DEG C
Electricity.
As shown in Figure 8, battery 10C fast charging and discharging persistent loop of the present invention 200 weeks, capability retention reaches more than 92%.
Claims (10)
1. a cathode size, it is characterised in that: include the component of following weight proportion: hard carbon and graphite compound 91-95%,
Conductive black 1-3%, Kynoar 4-6%, separately add the oxalic acid of total counterweight 0.1-0.3% of above-mentioned material.
Cathode size the most according to claim 1, it is characterised in that: in described hard carbon and graphite compound, hard carbon accounts for mixing
Material gross weight ratio is for 10-18%.
Cathode size the most according to claim 1, it is characterised in that: described hard carbon is micron particles, and its specific surface is
3-5m2/g。
Cathode size the most according to claim 1, it is characterised in that: described cathode size includes the group of following weight proportion
Part: hard carbon and graphite compound 94%, conductive black 1.5%, Kynoar 4.5%, separately add the grass of the total counterweight of above-mentioned material 0.2%
Acid；Wherein, hard carbon accounts for the weight ratio of compound is 15%.
5. according to the preparation method of the cathode size described in claim 1-4 any one, it is characterised in that: include walking as follows
Rapid:
1), vacuum drying step, take hard carbon and graphite compound, conductive black, Kynoar and the grass of above-mentioned weight proportion
Acid, as the raw material of cathode size, vacuum drying；
2), colloidal sol step, take N-Methyl pyrrolidone equiponderant with above-mentioned raw materials as solvent, by 1) in polyvinylidene fluoride
Alkene is dissolved in wherein, high-speed stirred；
3), to step 2) in preparation glue in add conductive black, stirring at low speed, obtain compound；
4) compound, in step 3) is initially charged hard carbon, stirring at low speed, obtains compound；
5) compound, in step 4) adds graphite, stirring at low speed, obtains compound；
6) compound, in step 5) adds oxalic acid, stirring at low speed, obtains compound；
7) the compound vacuum pressurize, by step 5) obtained, prepares cathode size；
Wherein vacuum is-0.09Mpa, and the dwell time is 1h.
The preparation method of cathode size the most according to claim 5, it is characterised in that: step 2) in sol-process, first
Not open cycle water, when temperature reaches 50 DEG C, then opens recirculated water, and when having stirred, glue is without substantially caking；Mixing time is 3
～4h.
The preparation method of cathode size the most according to claim 5, it is characterised in that: in step 3)-step 5) during stirring
Between be 1 h.
8. the negative plate prepared according to the cathode size described in claim 1-4 any one, it is characterised in that: described negative plate
Including negative current collector, in the upper and lower surface of negative current collector, even spread has cathode size.
Negative plate the most according to claim 8, it is characterised in that: the one side surface density of cathode size coating is 5.41-
6.41mg/cm2。
Lithium ion battery prepared by negative plate the most according to claim 8, it is characterised in that: include positive plate and negative pole
Sheet, described positive plate and negative plate all use full lug to design.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109742339A (en) * | 2018-12-14 | 2019-05-10 | 江苏海四达电源股份有限公司 | A kind of high-energy-density ultralow temperature high-safety polymer lithium ion battery and preparation method thereof |
| CN113471404A (en) * | 2020-03-15 | 2021-10-01 | 深圳格林德能源集团有限公司 | Inorganic ceramic coating negative plate of lithium ion battery and manufacturing method thereof |
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| CN103441305A (en) * | 2013-08-27 | 2013-12-11 | 深圳市贝特瑞新能源材料股份有限公司 | Power and energy storage lithium-ion battery and preparation method thereof |
| CN104577042A (en) * | 2014-12-23 | 2015-04-29 | 山东精工电子科技有限公司 | Lithium ion battery negative electrode paste and preparation method |
| CN104900904A (en) * | 2015-05-25 | 2015-09-09 | 深圳市斯盛能源股份有限公司 | Lithium ion secondary battery |
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Patent Citations (3)
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| CN103441305A (en) * | 2013-08-27 | 2013-12-11 | 深圳市贝特瑞新能源材料股份有限公司 | Power and energy storage lithium-ion battery and preparation method thereof |
| CN104577042A (en) * | 2014-12-23 | 2015-04-29 | 山东精工电子科技有限公司 | Lithium ion battery negative electrode paste and preparation method |
| CN104900904A (en) * | 2015-05-25 | 2015-09-09 | 深圳市斯盛能源股份有限公司 | Lithium ion secondary battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109742339A (en) * | 2018-12-14 | 2019-05-10 | 江苏海四达电源股份有限公司 | A kind of high-energy-density ultralow temperature high-safety polymer lithium ion battery and preparation method thereof |
| CN113471404A (en) * | 2020-03-15 | 2021-10-01 | 深圳格林德能源集团有限公司 | Inorganic ceramic coating negative plate of lithium ion battery and manufacturing method thereof |
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Application publication date: 20161130 |