CN105449265B - Safe lithium ion secondary cell - Google Patents

Safe lithium ion secondary cell Download PDF

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Publication number
CN105449265B
CN105449265B CN201510211876.5A CN201510211876A CN105449265B CN 105449265 B CN105449265 B CN 105449265B CN 201510211876 A CN201510211876 A CN 201510211876A CN 105449265 B CN105449265 B CN 105449265B
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lithium ion
ion secondary
diaphragm
battery
positive
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CN105449265A (en
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范财政
乔亚非
赵悠曼
程建良
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Shenzhen Cham New Energy Co Ltd
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Shenzhen Cham New Energy Co Ltd
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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
    • 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
    • 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
    • H01M4/48—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
    • 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
    • H01M4/48—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
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a kind of safe lithium ion secondary cells comprising anode and diaphragm, wherein the positive coating of the anode includes positive electrode, conductive agent and binder, and the positive electrode is ternary material LiNi1‑X‑YMnXCoYO2With iron manganese phosphate for lithium LiMnZFe1‑ZPO4Mixture, and the LiNi1‑X‑YMnXCoYO2With LiMnZFe1‑ZPO4Weight ratio be (4-9): 1；The longitudinal tensile strength of the diaphragm is greater than or equal to 1600kgf/cm2, transverse tensile strength is more than or equal to 1000kgf/cm2Diaphragm.Safe lithium ion secondary cell of the present invention can be tested effectively by the heavy impact of battery, improve the security performance of lithium ion secondary battery, while assigning the higher battery capacity of safe lithium ion secondary cell of the present invention and cycle performance.

Description

Safe lithium ion secondary cell
Technical field
The invention belongs to technical field of lithium ion secondary, in particular to a kind of safe lithium ion secondary cell.
Background technique
The characteristics of positive electrode that the power battery of electric car uses at present is ternary material mostly, the material is specific volume Amount is high, theoretical specific capacity 270mAh/g, and specific capacity is in 150-160mAh/g in actual use.The shortcomings that positive electrode is exactly to pacify Full performance is lower, causes heavy impact test that cannot pass through, and easily leads to power battery and explosive combustion occurs in the events such as collision. The combustion incident for causing power battery to explode such as the collision of domestic electric car generation recently.
Heavy impact test is the important safety test of electric vehicle battery, it is that simulated battery is hit in curved surface Situation come test battery whether safety, power battery on automobile using have often heavy impact test simulation the case where, So can be an important safety standard of automobile power battery by heavy impact test.
In order to improve the security performance of power battery, battery heavy impact performance is improved, is had at present by improving electrical resistance method Ability of anti-deformation attempts to improve battery heavy impact performance with the modes such as positive electrode content are changed, specific as used control The content of lithium iron manganese phosphate anode material improves battery heavy impact performance, and the theoretical specific capacity of iron manganese phosphate lithium material 170mAh/g, only 120-130mAh/g in actual use.Therefore, though the lithium iron manganese phosphate anode material have security performance compared with Good, cycle performance is excellent, generates heat when short-circuit few, but a disadvantage is that specific capacity is relatively low, therefore, in order to guarantee battery security Energy and capacity, can only be added the iron manganese phosphate of 10%~20% (weight ratio) in battery positive electrode active material (NCM and LMFP) Lithium, but heavy impact can't be effectively solved the problems, such as in this proportional region.A relevant patent document with the present invention 10~50 parts of 50~90 parts of nickel-cobalt-manganese ternary material, iron manganese phosphate for lithium blended anode materials being mixed to form are disclosed, by Soft-package battery made by the blended anode material can only solve safe needle pierce, overcharge, hot tank, but the invention be added Iron manganese phosphate for lithium is more, though improving certain security performance, capacity decreases, and effectively battery cannot be passed through Heavy impact test request, to improve the security performance of battery.
The risk of internal short-circuit of battery when though the mode for improving electrical resistance method ability of anti-deformation is easily reduced heavy impact.But Discovery, which relies solely on raising electrical resistance method ability of anti-deformation, in research and practical application still not can solve heavy impact problem.
Summary of the invention
It is an object of the invention to overcome the above-mentioned deficiency of the prior art, a kind of safe lithium ion secondary cell is provided, With the technical problem for overcoming the anti-heavy impact safety of existing lithium ion low.
In order to achieve the above-mentioned object of the invention, technical scheme is as follows:
A kind of safe lithium ion secondary cell, including anode and diaphragm, the positive coating of the anode include positive material Material, conductive agent and binder.Wherein, the positive electrode is ternary material LiNi1-X-YMnXCoYO2With iron manganese phosphate for lithium LiMnZFe1-ZPO4Mixture, and the LiNi1-X-YMnXCoYO2With LiMnZFe1-ZPO4Weight ratio be (4-9): 1, wherein 0 < X < 1,0 < Y < 1,0.5 < Z < 0.7；The longitudinal tensile strength of the diaphragm is greater than or equal to 1600kgf/cm2, cross directional stretch is strong Degree is greater than or equal to 1000kgf/cm2Diaphragm.
Aforementioned present invention safe lithium ion secondary cell passes through with LiNi1-X-YMnXCoYO2Ternary material with LiMnZFe1-ZPO4Iron manganese phosphate lithium mixture is positive pole material, and selects the specific diaphragm of certain strength, so that containing specific The anode of composite positive pole acts synergistically with diaphragm, and safe lithium ion secondary cell of the present invention is effectively passed through The heavy impact of battery is tested, and improves the security performance of lithium ion secondary battery, while assigning safe lithium ion two of the present invention The higher battery capacity of primary cell and cycle performance.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples, in attached drawing:
Fig. 1 is the capacity distribution map for the safe lithium ion secondary cell that the embodiment of the present invention 1 provides；
Fig. 2 is the capacity distribution map for the safe lithium ion secondary cell that the embodiment of the present invention 2 provides；
Fig. 3 is the capacity distribution map for the lithium ion secondary battery that comparative example 1 provides；
Fig. 4 is the capacity distribution map for the lithium ion secondary battery that comparative example 2 provides；
Fig. 5 is the capacity distribution map for the lithium ion secondary battery that comparative example 3 provides；
Fig. 6 is the capacity distribution map for the lithium ion secondary battery that comparative example 4 provides；
Fig. 7 is the charge and discharge cycles figure for the safe lithium ion secondary cell that the embodiment of the present invention 1 provides；
Fig. 8 is the charge and discharge cycles figure for the safe lithium ion secondary cell that the embodiment of the present invention 2 provides；
Fig. 9 is the charge and discharge cycles figure for the lithium ion secondary battery that comparative example 1 provides；
Figure 10 is the charge and discharge cycles figure for the lithium ion secondary battery that comparative example 2 provides；
Figure 11 is the charge and discharge cycles figure for the lithium ion secondary battery that comparative example 3 provides；
Figure 12 is the charge and discharge cycles figure for the lithium ion secondary battery that comparative example 4 provides.
Specific embodiment
In order to which technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with Embodiment and attached drawing, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used To explain the present invention, it is not intended to limit the present invention.
The embodiment of the present invention provides a kind of safe lithium ion secondary cell that can effectively test by heavy impact.The peace Holotype lithium ion secondary battery includes anode, cathode, diaphragm.The positive electrode, the negative electrode and the separator three is secondary according to conventional lithium ion Battery carries out assembling setting.It is axiomatic that lithium ion secondary battery of the embodiment of the present invention further includes necessary other component, Since other component is not the invention improvement of the embodiment of the present invention, other component is not repeated herein.
Wherein, the anode in lithium ion secondary battery of the embodiment of the present invention includes collector and is formed in the afflux body surface The positive electrode coating in face.The positive electrode coating includes the components such as positive electrode, conductive agent and binder.
In one embodiment, which is ternary material LiNi1-X-YMnXCoYO2(0 < X < 1,0 < Y < 1) (NCM) and phosphorus Sour manganese iron lithium LiMnZFe1-ZPO4The mixture of (0.5 < Z < 0.7) (LMFP), and the LiNi1-X-YMnXCoYO2With LiMnZFe1- ZPO4Weight ratio be (4-9): 1.By controlling the ratio of the ternary material and iron manganese phosphate for lithium, the battery that can be effectively improved is anti- Heavy impact performance improves the security performance of battery.
In a further embodiment, the ternary material and iron manganese phosphate for lithium mix the positive electrode of object composition in the positive material Expect that the weight percentage in coating is 93-97%.In certain embodiments, which applies in the positive electrode Weight percentage in layer can be 93%, 94%, 95%, 96%, 97%.By adjusting the ternary material and iron manganese phosphate Lithium mixes content of the positive electrode in positive coating of object composition, the energy while battery that effectively improves anti-heavy impact performance Battery is effectively improved, the battery capacity and cycle performance of battery are improved.
In one embodiment, weight percentage control of the conductive agent in the positive electrode coating is 1.5%- 2%.Content by controlling conductive agent can effectively cooperate the mixing above being made of ternary material and the mixed object of iron manganese phosphate for lithium The electric conductivity that anode can be effectively improved while the battery anti-heavy impact performance that object positive electrode improves, to improve battery Chemical property.In order to further increase the performance, in certain embodiments, which selects conductive black, surpasses Lead at least one of carbon black, graphite-like, carbon nanotube.In a particular embodiment, conductive agent select acetylene black, Super-P, KS-6,305G, CNT etc.
In one embodiment, weight percentage of the binder in the positive coating is 1.6%-2%.Pass through The content of control binder can be effectively controlled the surface density and electrode slice sound construction intensity of positive plate, at the same cooperate it is above by Ternary material and iron manganese phosphate for lithium mix the anti-heavy impact performance of battery that the mixture positive electrode of object composition improves.In order into one Step improves the performance, and in certain embodiments, which selects Kynoar (PVDF), Kynoar-hexafluoro At least one of propylene (PVDF-HFP), polytetrafluoroethylene (PTFE) (PTFE).
In one embodiment, described above to contain ternary material LiNi1-X-YMnXCoYO2With iron manganese phosphate for lithium LiMnZFe1-ZPO4Mixture anode preparation method it is as follows:
Step S01: after binder and solvent are proportionally mixed, it is configured to glue；
Step S02: conductive agent is added in the glue prepared to step S01 and carries out mixing treatment, is configured to the first mixing Slurry；
Step S03: LiMn is added in the first mixed slurry prepared to step S02ZFe1-ZPO4Iron manganese phosphate for lithium simultaneously carries out Mixing treatment is configured to the second mixed slurry；
Step S04: LiNi is added in the second mixed slurry prepared to step S031-X-YMnXCoYO2Ternary material simultaneously carries out Mixing treatment is configured to anode sizing agent；
Step S05: the anode sizing agent coating that step S04 is prepared on a current collector, forms anode.
Wherein, the solvent in above-mentioned steps S01 can be selected but be not limited only to N-Methyl pyrrolidone (NMP).It is prepared Gelatin concentration, that is to say that the ratio of binder and solvent can be prepared according to ratio in Examples below 1.In order to enable Glue is uniform, and in one embodiment, stirring condition when preparing glue is 100~120r/min of revolution, and rotation 2000~ 3000r/min, 1.5~2h of time.
In one embodiment, the condition of mixing treatment is 100~120r/min of revolution, rotation 3000 in above-mentioned steps S02 ~5000r/min, 1.5~2h of time.The condition of the mixing treatment can make conductive agent fully dispersed.
In one embodiment, the condition of mixing treatment is 100~120r/min of revolution, rotation 3000 in above-mentioned steps S03 ~5000r/min, 0.5~1h of time.In another embodiment, in above-mentioned steps S04 mixing treatment condition be revolution 100~ 120r/min, 3000~5000r/min of rotation, 0.5~1h of time.It is controlled, can be made each by the condition of above-mentioned mixing treatment Component is sufficiently mixed, to form uniform anode sizing agent.
The mode of anode sizing agent coating on a current collector can be applied in a conventional manner in above-mentioned steps S05 Cloth.After to be coated, natural further includes the steps that other subsequent processings such as dry to anode.
Positive diaphragm in lithium ion secondary battery of the embodiment of the present invention above selects longitudinal tensile strength to be greater than or equal to 1600kgf/cm2, transverse tensile strength is more than or equal to 1000kgf/cm2Diaphragm.By the control to membrane performance, make it It acts synergistically with the anode containing specific composite positive pole with diaphragm, so that safe lithium ion secondary cell of the present invention It can effectively be tested by the heavy impact of battery, improve the security performance of lithium ion secondary battery.
In order to further increase the ability of anti-deformation of battery of the embodiment of the present invention, improve the anti-heavy impact performance of battery with And corresponding chemical property, in a further embodiment, the diaphragm selects polyethylene, polypropylene, in Kynoar It is any.In another embodiment, the thickness control of the diaphragm is 18-22 μm, in one embodiment, the thickness of the diaphragm Degree control is 20 μm.
Aforementioned present invention safe lithium ion secondary cell passes through multiple with ternary material and two positive electrode of iron manganese phosphate for lithium It closes and uses, and control the ratio of the two, so that the anode containing specific composite positive pole acts synergistically with diaphragm, so that Safe lithium ion secondary cell of the present invention can be tested effectively by the heavy impact of battery, and the peace of lithium ion secondary battery is improved Full performance, while assigning the higher battery capacity of safe lithium ion secondary cell of the present invention and cycle performance.
Now by taking safe lithium ion secondary cell of the embodiment of the present invention as an example, the present invention will be described in further detail.
Embodiment 1
The positive coating of a kind of safe lithium ion secondary cell, anode includes LiNi1-X-YMnXCoYO2(NCM): LiMnZFe1-ZPO4(LMFP): acetylene black: PVDF=91.2:4.8:2:2.20 μm of the thickness of diaphragm, transverse tensile strength are 1000kgf/cm2, longitudinal tensile strength 1600kgf/cm2。
The safe lithium ion secondary cell the preparation method is as follows:
Step S11: by PVDF and NMP, the glue of weight ratio PVDF:NMP=5:95 is stirred into conjunction pulp grinder, wherein PVDF Weight determined according to the 2% of positive total material.Mixing parametric: revolution 100~120r/min, 2000~3000r/min of rotation, 1.5~2h of time；
Step S12: the acetylene black of positive total material 2% (weight ratio) is added.Mixing parametric: 100~120r/min of revolution, from Turn 3000~5000r/min, 1.5~2h of time；
Step S13: 4.8% that LMFP weight is positive total material is added, mixing parametric: 100~120r/min of revolution, rotation 3000~5000r/min, 0.5~1h of time；
Step S14: 91.2% mixing parametric that NCM weight is positive total material: 100~120r/min of revolution, rotation is added 3000~5000r/min, 3~4h of time；
Step S15: the slurry got togather above is coated, and makes positive plate, then selects corresponding cathode, and cooperation is thick 20 μm of degree, transverse tensile strength is 1000kgf/cm2Diaphragm, be fabricated to 18650 type batteries.
Embodiment 2
The positive coating of a kind of safe lithium ion secondary cell, anode includes LiNi1-X-YMnXCoYO2:LiMnZFe1- ZPO4: acetylene black: PVDF=76.8:19.2:2:2.20 μm of the thickness of diaphragm, transverse tensile strength is 1000kgf/cm2, longitudinal Tensile strength 1600kgf/cm2。
The preparation method of the present embodiment safe lithium ion secondary cell is referring to embodiment 1.
Comparative example 1
The positive coating of a kind of lithium ion secondary battery, anode includes LiNi1-X-YMnXCoYO2:LiMnZFe1-ZPO4: second Acetylene black: PVDF=86.4:9.6:2:2.20 μm of the thickness of diaphragm, transverse tensile strength is 800kgf/cm2, longitudinal tensile strength 1600kgf/cm2。
The preparation method of the present embodiment lithium ion secondary battery is referring to embodiment 1.
Comparative example 2
The positive coating of a kind of lithium ion secondary battery, anode includes LiNi1-X-YMnXCoYO2:LiMnZFe1-ZPO4: second Acetylene black: PVDF=76.8:19.2:2:2.20 μm of the thickness of diaphragm, transverse tensile strength is 800kgf/cm2, longitudinal tensile strength 1600kgf/cm2。
The preparation method of the present embodiment lithium ion secondary battery is referring to embodiment 1.
Comparative example 3
The positive coating of a kind of lithium ion secondary battery, anode includes LiNi1-X-YMnXCoYO2: acetylene black: PVDF= 96:2:2.20 μm of the thickness of diaphragm, transverse tensile strength is 1000kgf/cm2, longitudinal tensile strength 1600kgf/cm2。
The preparation method of the present embodiment lithium ion secondary battery is referring to embodiment 1.
Comparative example 4
The positive coating of a kind of lithium ion secondary battery, anode includes LiNi1-X-YMnXCoYO2:LiMnZFe1-ZPO4: second Acetylene black: PVDF=91.2:4.8:2:2.20 μm of the thickness of diaphragm, transverse tensile strength is 1000kgf/cm2, longitudinal tensile strength 1600kgf/cm2。
Correlated performance test
1. lithium ion secondary battery capacity is tested:
The above embodiments 1-2 and comparative example the 1-4 lithium ion secondary battery provided are surveyed according to UL1642 respectively Test-object standard carries out battery capacity test, and test result is as follows:
Test results are shown in figure 1 for battery capacity in embodiment 1, battery capacity test result such as Fig. 2 in embodiment 2 Shown, the battery capacity test result difference in comparative example 1-4 is as seen in figures 3-6.
2. the heavy impact performance test of lithium ion secondary battery:
By the above embodiments 1-2 and comparative example the 1-4 lithium ion secondary battery provided take respectively 10 samples according to UL1642 testing standard carries out the performance test of battery heavy impact, and test result is as follows:
Heavy impact the performance test results in embodiment 1 are as shown in table 1 and table 7:
Table 1
Battery 1# 2# 3# 4# 5# 6# 7# 8# 9# 10#
Phenomenon Leakage Leakage Leakage Leakage Leakage Leakage Leakage Leakage Leakage Leakage
Heavy impact the performance test results in embodiment 2 are as shown in table 2 and table 7:
Table 2
Battery 1# 2# 3# 4# 5# 6# 7# 8# 9# 10#
Phenomenon Leakage Leakage Leakage Leakage Leakage Leakage Leakage Leakage Leakage Leakage
Heavy impact the performance test results in comparative example 1 are as shown in table 3 and table 7:
Table 3
Battery 1# 2# 3# 4# 5# 6# 7# 8# 9# 10#
Phenomenon Leakage It is on fire Leakage Leakage Leakage Leakage It is on fire It is on fire Leakage Leakage
Heavy impact the performance test results in comparative example 2 are as shown in table 4 and table 7:
Table 4
Battery 1# 2# 3# 4# 5# 6# 7# 8# 9# 10#
Phenomenon It is on fire Leakage Leakage Leakage Leakage It is on fire Leakage Leakage Leakage Leakage
Heavy impact the performance test results in comparative example 3 are as shown in table 5 and table 7:
Table 5
Battery 1# 2# 3# 4# 5# 6# 7# 8# 9# 10#
Phenomenon It is on fire It is on fire It is on fire It is on fire Explosion It is on fire It is on fire Explosion Leakage It is on fire
Heavy impact the performance test results in comparative example 4 are as shown in table 6 and table 7:
Table 6
Battery 1# 2# 3# 4# 5# 6# 7# 8# 9# 10#
Phenomenon It is on fire Leakage Leakage It is on fire It smolders It is on fire It is on fire Leakage Leakage It smolders
The weight punching of the lithium ion secondary battery in lithium ion secondary battery capacity test and the comprehensive 2nd in average 1st It is as shown in table 7 below to hit the performance test results:
LMFP:NCM (weight ratio) Capacity mean value (mAh) Heavy impact test
Embodiment 1 1:9 2182.4 Pass through
Embodiment 2 1:4 2080.3 Pass through
Comparative example 1 1:9 2152.8 Do not pass through
Comparative example 2 1:4 2209.1 Do not pass through
Comparative example 3 —— 2234.8 Do not pass through
Comparative example 4 1:19 2207.2 Do not pass through
3. the charge-discharge performance of lithium ion secondary battery is tested:
The lithium ion secondary battery that the above embodiments 1-2 and comparative example 1-4 are provided is respectively according to following condition Carry out charge-discharge performance test:
Charging: electric current 0.5C, blanking voltage 4.2V, cut-off current 0.02C；
Electric discharge: electric current 1C, blanking voltage 3V.
Charge-discharge performance test result difference in embodiment 1-2 is as shown in Figure 7,8, in comparative example 1-4 Battery capacity test result difference is as shown in figs9-12.
Known to comprehensive analysis above-mentioned Fig. 1-12 and table 1-7:
LMFP:NCM=1:9 in embodiment 1, and the transverse tensile strength 1000kgf/cm of diaphragm2It can effectively solve Heavy impact problem.After cycle performance preferably recycles 428 times, capacity retention ratio is 92.7%.
LMFP:NCM=1:4 in embodiment 2, and the transverse tensile strength 1000kgf/cm of diaphragm2It can solve weight Shock problem, but because of the increase of LMFP, battery capacity decreases.
LMFP:NCM=1:9 in comparative example 1, compared with Example 1, the transverse tensile strength of diaphragm are reduced to 800kgf/cm2, heavy impact problem do not solve, and illustrates LMFP in the case where this weight ratio, reduces the lateral of diaphragm and draws Stretching intensity not can solve problem.
LMFP:NCM=1:4 in comparative example 2 increases the ratio of LMFP, but do not solve compared with comparative example 1 Certainly problem illustrates that in the transverse tensile strength of diaphragm be 800kgf/cm2Under conditions of, the ratio raising of LMFP can not be solved Certainly problem.
That LMFP is not added in comparative example 3, compared with Example 1, the transverse tensile strength of diaphragm is identical, weight punching It hits problem not solve, illustrates that diaphragm transverse tensile strength is 1000kgf/cm2When, being added without LMFP not can solve problem.
LMFP additional amount is less in comparative example 4, but the transverse tensile strength 1000kgf/cm of diaphragm2, instruction sheet The tensile strength for solely improving diaphragm can not solve the problems, such as.
Therefore, in embodiments of the present invention, by controlling the ratio of LMFP and NCM, while by diaphragm mechanical property Control so that play synergistic function between blended anode material and diaphragm, to effectively improve peace of the embodiment of the present invention The anti-heavy impact performance of holotype lithium ion secondary battery, improves its security performance, in addition, being also adjustable and assigning the present invention Embodiment safe lithium ion secondary cell excellent capacity and charge-discharge performance.Specifically, pass through the experiment in the 1 to the 3rd Data are prepared it is found that limiting range in the embodiment of the present invention, although the increase with LMFP content causes the capacity of battery to successively decrease, But the anti-heavy impact performance of battery is being improved.The ratio for illustrating NCM and LMFP by heavy impact test result is 9: 1-4:1 (weight ratio), and diaphragm longitudinal tensile strength is greater than 1600kgf/cm2, transverse tensile strength is greater than 1000kgf/cm2When It can effectively solve the problem of battery heavy impact test difficulty passes through.In a preferred embodiment, LMFP and NMP in the embodiment of the present invention Preferred ratio is 1:9, while the preferred 1000kgf/cm of transverse tensile strength of diaphragm2。
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.

Claims (2)

1. a kind of safe lithium ion secondary cell comprising anode and diaphragm, the positive coating of the anode include positive material Material, conductive agent and binder, it is characterised in that: the positive electrode is ternary material LiNi1-X-YMnXCoYO2With iron manganese phosphate for lithium LiMnZFe1-ZPO4Mixture, the conductive agent is acetylene black, and the binder is PVDF, and the LiNi1-X-YMnXCoYO2 With LiMnZFe1-ZPO4It is 91.2:4.8:2:2 with the acetylene black and the weight ratio of PVDF, wherein 0 < X < 1,0 < Y < 1,0.5 < Z<0.7；The longitudinal tensile strength of the diaphragm is 1600kgf/cm2, transverse tensile strength 1000kgf/cm2；The diaphragm Thickness control is 20 μm；
The safe lithium ion secondary cell is to be prepared as follows:
The PVDF and NMP: being stirred into the glue of weight ratio PVDF:NMP=5:95 by S11 with conjunction pulp grinder, wherein the weight of PVDF 2% according to positive total material is measured to determine；Mixing parametric: revolve 100~120r/min, 2000~3000r/min of rotation, the time 1.5~2h；
S12: the acetylene black of 2% weight ratio of positive total material is added；Mixing parametric: 100~120r/min of revolution, rotation 3000~ 5000r/min, 1.5~2h of time；
S13: LiMn is addedZFe1-ZPO4Weight is the 4.8% of positive total material, mixing parametric: 100~120r/min of revolution, rotation 3000~5000r/min, 0.5~1h of time；
S14: LiNi is added1-X-YMnXCoYO2Weight is 91.2% mixing parametric of positive total material: 100~120r/min of revolution, from Turn 3000~5000r/min, 3~4h of time；
S15: slurry is coated, and makes positive plate, then selects corresponding cathode, cooperates 20 μm of thickness, cross directional stretch is strong Degree is 1000kgf/cm2Diaphragm, be fabricated to 18650 type batteries.
2. safe lithium ion secondary cell according to claim 1, it is characterised in that: the diaphragm selection polyethylene, Any one of polypropylene, Kynoar.
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