CN101667661A - 一种匹配锂离子二次电池天然石墨负极的电解液 - Google Patents
一种匹配锂离子二次电池天然石墨负极的电解液 Download PDFInfo
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- 229910021382 natural graphite Inorganic materials 0.000 title claims abstract description 34
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 20
- 239000008151 electrolyte solution Substances 0.000 title abstract 3
- 239000003792 electrolyte Substances 0.000 claims abstract description 33
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052796 boron Inorganic materials 0.000 claims abstract description 20
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 6
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 4
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 4
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 4
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 4
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 229910052718 tin Inorganic materials 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000000654 additive Substances 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 8
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 229910052730 francium Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 230000007774 longterm Effects 0.000 abstract description 5
- 150000001639 boron compounds Chemical class 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 239000002131 composite material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
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Abstract
本发明提供了一种匹配锂离子二次电池天然石墨负极的电解液,含有有机溶剂和锂盐电解质,电解液还含有含硼元素化合物的添加剂。含硼元素化合物的化学式为:AxByCzDw:其中A元素为碱金属,x值范围为0≤x≤4;B元素为硼元素,y值范围为0≤y≤4;C元素为:C,Si,Ge,Sn,N,P,As,S,Se之其中一种,z值范围为0≤z≤8;D元素为:N,O,S,F,Cl,Br之其中一种,w值范围为:0≤w≤32。本发明的匹配天然石墨类负极锂离子电池用电解液与天然石墨负极具有更好的成膜特性,能够优化负极SEI膜的形态,其具有与锂离子电池的天然石墨负极极好的匹配作用,提高了电池的长期储存与循环使用寿命。
Description
技术领域
本发明涉及高能电池技术领域,特别是关于一种匹配锂离子二次电池天然石墨负极的电解液。
背景技术
随着市场对高比容量锂离子电池需求的增加,天然石墨类负极材料得到了广泛应用,但天然石墨类负极材料整体电池具有长期储存以及循环性能较差的缺点,因而需要改善整体锂离子电池循环性能等电化学性能。现有技术现状是:天然石墨负极类整体电池,虽然具有较高体积比容量,但整体电池循环性能较差,300次循环容量保持率一般不超过85%。
发明内容
本发明的目的是提供一种电解液,其具有与锂离子电池的天然石墨负极具有极好的匹配作用,提高了电池的长期储存与循环使用寿命。
本发明提供了一种匹配锂离子二次电池天然石墨负极的电解液,含有有机溶剂和锂盐电解质,所述电解液还含有含硼元素化合物的添加剂。
所述的含硼元素化合物的化学式为:AxByCzDw:其中
A元素为碱金属,x值范围为0≤x≤4;
B元素为硼元素,y值范围为0≤y≤4;
C元素为:C,Si,Ge,Sn,N,P,As,S,Se之其中一种,z值范围为0≤z≤8;
D元素为:N,O,S,F,Cl,Br之其中一种,w值范围为:0≤w≤32。
所述的A元素为Li,Na,K,Ru,Se,Fr之其中一种。
所述含硼元素化合物BF3或B2O3。
所述的含硼元素化合物占总重量的0.1%~10%。
所述的有机溶剂成份及各成份的质量比为:EC/EMC/DMC/DEC/PC=3/2/2/2/1;电解质锂盐为LiPF6,浓度为1.1M。
本发明的电解液体系引入了复合负极成膜添加剂的含有硼元素类化合物添加剂,天然石墨负极与本电解液具有良好的成膜特性,优化了天然石墨负极SEI膜的物理化学性质,使得整体电池具有良好的电化学性能;整体电池1C倍率充放电循环800次,容量保持率在85%以上;本发明的电解液采用了新型添加剂体系,如含有硼元素化合物等;电解质体系为LiPF6(六氟磷酸锂);溶剂体系可以匹配EC(碳酸乙烯酯),PC(碳酸丙烯酯),DMC(碳酸二甲酯),EMC(碳酸甲乙酯),DEC(碳酸二乙酯)等。
本发明的匹配天然石墨类负极锂离子电池用电解液与天然石墨负极具有更好的成膜特性,能够优化负极SEI膜的形态,从而改善天然石墨负极整体电池的电化学性能如长期储存与循环使用寿命等。
具体实施方式
下面,将详细说明本发明的实施形态。本发明不限于实施形态。
本发明的电解液电解质体系为LiPF6;溶剂体系可以匹配EC(碳酸乙烯酯),PC(碳酸丙烯酯),DMC(碳酸二甲酯),EMC(碳酸甲乙酯),DEC(碳酸二乙酯)等其中一种或多种。为了解决天然石墨类负极锂离子电池储存与循环使用寿命较差的缺点,本发明在电解液中添加了新型添加剂体系:含有硼元素化合物。其中所述的含有硼元素化合物的化学式为:AxByCzDw:其中,
A元素为碱金属:如Li,Na,K,Ru,Se,Fr等,x值范围为0≤x≤4;
B元素为硼元素,y值范围为0≤y≤4;
C元素为:C,Si,Ge,Sn,N,P,As,S,Se等,z值范围为0≤z≤8;
D元素为:N,O,S,F,Cl,Br等,w值范围为:0≤w≤32。
匹配天然石墨负极整体锂离子电池,含硼元素化合物的电解液在首次充放电时,能够在天然石墨负极表面形成良好的SEI膜,含有B(硼)元素的SEI膜层具有良好的物理稳定性以及电化学稳定性,因而能够大幅改善天然石墨负极整体电池的电化学性能,如循环性能等。
下面举例说明本实施例中的添加有含硼元素化合物的电解液的成分及配比:
溶剂:EC/EMC/DMC/DEC/PC=3/2/2/2/1(质量比);
电解质锂盐:LiPF6,浓度为1.1M;
添加剂:以含硼元素化合物为主的复合添加剂,例如含有BF3,B2O3等硼元素化合物,单一化合物如BF3的添加量为0.1%~10%之间。
本发明的匹配天然石墨类负极锂离子电池用电解液与天然石墨负极具有更好的成膜特性,能够优化负极SEI膜的形态,从而改善天然石墨负极整体电池的电化学性能如长期储存与循环使用寿命等;
本发明通过加入含有硼元素类化合物添加剂可以解决天然石墨类负极锂离子电池储存与循环使用寿命较差的缺点,使得整体电池的使用寿命得到大幅提升。
常规电解液与本专利发明电解液整体电池循环数据对比如下:
1)本专发明电解液与天然石墨负极匹配整体电池循环数据:
整体电池为铝塑膜电池,标称容量180mA·h;正极为钴酸锂,负极为天然石墨,电解液体系为本专利所发明电解液;
首次放电容量为190mA·h;1C倍率800次循环后放电容量为164mA·h;容量保持率为86.3%;
循环序号 | 充电/mA·h | 放电/mA·h | 平台容量/mA·h |
1 | 211.4 | 189.9 | 179.1 |
2 | 192.9 | 190 | 159.2 |
3 | 190.5 | 189.4 | 159.4 |
4 | 189.6 | 188.7 | 158.8 |
5 | 188.6 | 187.8 | 156.4 |
6 | 188.9 | 188.4 | 160.9 |
7 | 188.6 | 188 | 161.1 |
8 | 188.2 | 187.4 | 160.9 |
9 | 187.7 | 187 | 161 |
10 | 187.2 | 187.1 | 161.3 |
11 | 187.2 | 186.9 | 160.8 |
12 | 186.9 | 186.7 | 160.7 |
13 | 186.8 | 186.4 | 160.4 |
14 | 186.8 | 186.5 | 162.3 |
15 | 187.4 | 187.2 | 164.9 |
16 | 187.5 | 187.2 | 165.2 |
17 | 187.9 | 187.5 | 166.5 |
18 | 187.6 | 187.4 | 165.7 |
19 | 187.3 | 187 | 165.4 |
20 | 186.8 | 186.5 | 163.9 |
21 | 186.8 | 186.5 | 164.5 |
22 | 186.6 | 186.2 | 164.1 |
23 | 186.3 | 186 | 164 |
24 | 186.2 | 186 | 164 |
25 | 186.4 | 186.2 | 164.6 |
26 | 186.4 | 185.9 | 165 |
27 | 186 | 185.7 | 164.8 |
28 | 186 | 185.8 | 164.4 |
29 | 185.8 | 185.5 | 163.7 |
30 | 185 | 184.9 | 162.5 |
31 | 185 | 184.8 | 163.3 |
32 | 185.4 | 185.1 | 163.7 |
33 | 185.1 | 184.9 | 163.3 |
34 | 185.2 | 185.1 | 164.2 |
35 | 185.1 | 184.8 | 163.6 |
36 | 185 | 184.9 | 163.7 |
37 | 184.9 | 184.6 | 163.7 |
38 | 184.8 | 184.6 | 163.4 |
39 | 184.7 | 184.5 | 162.9 |
40 | 184 | 184 | 162.6 |
41 | 184.4 | 184.2 | 162.7 |
42 | 184.2 | 184 | 162.4 |
43 | 183.9 | 183.8 | 162 |
44 | 184 | 183.8 | 162.4 |
45 | 184.1 | 184 | 162.6 |
46 | 183.9 | 183.7 | 162.4 |
47 | 183.8 | 183.6 | 162.4 |
48 | 183.8 | 183.7 | 162.5 |
49 | 183.8 | 183.6 | 162.5 |
50 | 183.7 | 183.5 | 162.5 |
51 | 183.6 | 183.5 | 161.9 |
52 | 183.5 | 183.2 | 162.2 |
53 | 183.3 | 183.2 | 162.1 |
54 | 183.3 | 183.2 | 162.3 |
55 | 183.3 | 183.2 | 162.2 |
56 | 183.3 | 183 | 162.2 |
57 | 183.1 | 182.9 | 161.5 |
58 | 182.9 | 182.7 | 160.6 |
59 | 182.5 | 182.5 | 160.5 |
60 | 182.8 | 182.6 | 160.8 |
61 | 182.6 | 182.6 | 160.6 |
62 | 182.6 | 182.3 | 160.3 |
63 | 182.3 | 182.3 | 159.8 |
64 | 182.3 | 182.1 | 159.7 |
65 | 174.8 | 182.1 | 160.7 |
66 | 182.4 | 182.4 | 161 |
67 | 182.4 | 182.2 | 160.7 |
68 | 182.2 | 182.1 | 160.7 |
69 | 182.1 | 181.8 | 160 |
70 | 181.8 | 181.9 | 159.9 |
71 | 182 | 181.8 | 159.8 |
72 | 181.8 | 181.8 | 159.4 |
73 | 181.7 | 181.6 | 159.3 |
74 | 181.8 | 181.6 | 159.6 |
75 | 181.5 | 181.5 | 159.4 |
76 | 181.6 | 181.6 | 159.6 |
77 | 181.6 | 181.5 | 159.6 |
78 | 181.7 | 181.6 | 160 |
79 | 181.6 | 181.4 | 159.6 |
80 | 181.5 | 181.4 | 159.6 |
81 | 181.4 | 181.2 | 159.5 |
82 | 181.2 | 181.2 | 158.9 |
83 | 181.2 | 181.1 | 158.9 |
84 | 181.4 | 181.3 | 159.9 |
85 | 181.4 | 181.3 | 159.4 |
86 | 181.3 | 181.2 | 160.3 |
87 | 181.2 | 181.2 | 160.2 |
88 | 181.3 | 181.2 | 160 |
89 | 181.1 | 181 | 160.1 |
90 | 181.1 | 180.9 | 159.4 |
91 | 180.9 | 180.8 | 159.4 |
92 | 180.8 | 180.6 | 159.1 |
93 | 180.7 | 180.6 | 159 |
94 | 180.6 | 180.4 | 158 |
95 | 180.5 | 180.3 | 157.9 |
96 | 180.4 | 180.3 | 157.7 |
96 | 180.4 | 180.3 | 157.7 |
97 | 180.2 | 180.2 | 157.7 |
98 | 180.5 | 180.3 | 159.1 |
99 | 180.4 | 180.2 | 157.8 |
100 | 180.1 | 179.9 | 158.2 |
101 | 180.3 | 180.1 | 158.4 |
102 | 180.2 | 180.2 | 158 |
103 | 180.3 | 180 | 157.9 |
104 | 180 | 179.8 | 156.7 |
105 | 179.6 | 179.5 | 155.3 |
106 | 179.6 | 179.3 | 155.2 |
107 | 179.5 | 179.4 | 155 |
108 | 179.3 | 179.2 | 154.9 |
109 | 179.1 | 178.8 | 153.3 |
110 | 178.8 | 178.7 | 153.2 |
111 | 178.8 | 178.7 | 153.2 |
112 | 178.7 | 178.6 | 152.8 |
113 | 178.4 | 178.3 | 151.8 |
114 | 178.8 | 178.8 | 155 |
115 | 179.2 | 179.1 | 156.2 |
116 | 179.1 | 179 | 155.7 |
117 | 179 | 178.9 | 155.6 |
118 | 179 | 179 | 156.2 |
119 | 179 | 178.9 | 154.9 |
120 | 178.6 | 178.4 | 152.7 |
121 | 178.1 | 177.9 | 151.7 |
122 | 177.6 | 177.4 | 149.1 |
123 | 177.3 | 177.3 | 148.4 |
124 | 177.9 | 177.9 | 152.5 |
125 | 178.5 | 178.6 | 155.7 |
126 | 178.7 | 178.5 | 155.9 |
127 | 178.7 | 178.6 | 156.1 |
128 | 178.7 | 178.6 | 155.8 |
129 | 178.6 | 178.3 | 154.7 |
130 | 177.9 | 177.7 | 151.9 |
131 | 177.8 | 177.5 | 151.3 |
132 | 177.5 | 177.4 | 150.6 |
133 | 177.3 | 177.1 | 150.3 |
134 | 177.2 | 177.1 | 150.4 |
135 | 177.3 | 177.1 | 150.3 |
136 | 177.1 | 177.1 | 150.2 |
137 | 177.1 | 177 | 151.7 |
138 | 177.3 | 177.2 | 151.7 |
139 | 177.3 | 177.1 | 151.6 |
140 | 177.2 | 177 | 151.6 |
141 | 177 | 177 | 150.9 |
142 | 177 | 176.8 | 150.4 |
143 | 176.8 | 176.8 | 150.2 |
144 | 176.9 | 177 | 152.5 |
145 | 177.4 | 177.2 | 153.2 |
146 | 177.3 | 177.2 | 153.1 |
147 | 177.4 | 177.2 | 153.1 |
148 | 177.5 | 178.5 | 155 |
149 | 177.3 | 177.4 | 154.2 |
150 | 177.6 | 177.4 | 154.6 |
151 | 177.5 | 177.4 | 154.2 |
152 | 177.4 | 177.3 | 153.6 |
153 | 177.2 | 177.1 | 153.2 |
154 | 177.2 | 176.9 | 153.3 |
155 | 177.5 | 177.7 | 156.2 |
156 | 177.9 | 177.9 | 158.1 |
157 | 178.6 | 178.4 | 159.6 |
158 | 173 | 178.8 | 160.3 |
159 | 178.7 | 178.4 | 158.8 |
160 | 178.3 | 178.2 | 158.3 |
161 | 178.2 | 178 | 157.6 |
162 | 178 | 177.9 | 157 |
163 | 177.8 | 177.7 | 156.4 |
164 | 177.6 | 177.4 | 156.2 |
165 | 177.6 | 177.6 | 156.7 |
166 | 178.1 | 178 | 158.3 |
167 | 178.1 | 178 | 159 |
168 | 178.2 | 178 | 159.8 |
169 | 178.1 | 178 | 159.2 |
170 | 178.1 | 178.1 | 158.6 |
171 | 178.1 | 177.8 | 158.3 |
172 | 174 | 178 | 158.9 |
173 | 178.1 | 177.9 | 158.4 |
174 | 177.9 | 177.9 | 158.2 |
175 | 177.6 | 177.4 | 156.5 |
176 | 177.7 | 177.6 | 158 |
177 | 177.9 | 177.7 | 158.7 |
178 | 177.8 | 177.8 | 158.8 |
179 | 178.2 | 178.1 | 160.3 |
180 | 178.3 | 178.2 | 159.3 |
181 | 177.7 | 177.6 | 157.6 |
182 | 177.7 | 177.6 | 158.4 |
183 | 177.8 | 177.6 | 158 |
184 | 177.6 | 177.4 | 158.1 |
185 | 177.5 | 177.3 | 157.1 |
186 | 177.4 | 177.3 | 157.3 |
187 | 177.6 | 177.5 | 158.6 |
188 | 177.7 | 177.7 | 158.6 |
189 | 177.7 | 177.6 | 158.7 |
190 | 177.8 | 177.6 | 158.6 |
191 | 177.5 | 177.3 | 157.1 |
192 | 177.2 | 177.1 | 157.6 |
193 | 177.4 | 177.3 | 157.9 |
194 | 177.4 | 177.2 | 157.6 |
195 | 177.2 | 177.1 | 157.3 |
196 | 176.9 | 176.7 | 155.8 |
197 | 176.8 | 176.9 | 157.1 |
198 | 177.1 | 177.1 | 157.5 |
199 | 177.3 | 177.2 | 157.9 |
200 | 177.3 | 177.2 | 158.1 |
201 | 177.2 | 177.1 | 157.8 |
202 | 177.2 | 177 | 157.1 |
203 | 176.9 | 176.7 | 157.1 |
204 | 176.8 | 176.8 | 157.2 |
205 | 176.9 | 176.8 | 157.1 |
206 | 176.8 | 176.6 | 156.4 |
207 | 176.7 | 176.6 | 156.3 |
208 | 176.6 | 176.5 | 156.3 |
209 | 176.6 | 176.4 | 155.1 |
210 | 176.3 | 176.2 | 155.7 |
211 | 176.3 | 176.1 | 155.9 |
212 | 176.4 | 176.3 | 155.5 |
213 | 176.2 | 176 | 154.8 |
214 | 176 | 176 | 154.5 |
215 | 176 | 175.8 | 154.3 |
216 | 175.9 | 175.7 | 153.8 |
217 | 175.8 | 175.7 | 154.4 |
218 | 175.9 | 175.8 | 154.4 |
219 | 175.8 | 175.7 | 153.4 |
220 | 175.7 | 175.5 | 153 |
221 | 175.5 | 175.3 | 152.7 |
222 | 175.2 | 175 | 151.3 |
223 | 175 | 174.9 | 151.6 |
224 | 175 | 175 | 152 |
225 | 175.1 | 175 | 152.1 |
226 | 175 | 175.2 | 155 |
227 | 176.3 | 176.2 | 156.6 |
228 | 175.8 | 175.5 | 155.8 |
229 | 175.4 | 175.3 | 153.4 |
230 | 175.3 | 175.1 | 153.1 |
231 | 175.2 | 175.1 | 153 |
232 | 175.2 | 175.1 | 152.9 |
233 | 175 | 174.8 | 150.5 |
234 | 174.9 | 174.9 | 150.4 |
235 | 174.9 | 174.8 | 150.4 |
236 | 174.9 | 174.6 | 150.4 |
237 | 174.6 | 174.6 | 150.2 |
238 | 174.7 | 174.7 | 151.1 |
239 | 175 | 174.9 | 151.9 |
240 | 175 | 174.9 | 152.9 |
241 | 175.2 | 175 | 153.5 |
242 | 175.2 | 175.1 | 153.3 |
243 | 175.3 | 175.2 | 152.9 |
244 | 175.2 | 175.1 | 152.8 |
245 | 175.1 | 175 | 152.6 |
246 | 175 | 174.9 | 152.1 |
247 | 175 | 174.8 | 152.1 |
248 | 174.8 | 174.8 | 151.9 |
249 | 175 | 175.1 | 153.7 |
250 | 175.5 | 175.4 | 154.9 |
251 | 175.6 | 175.6 | 155.7 |
252 | 175.7 | 175.5 | 155.2 |
253 | 175.5 | 175.3 | 154.5 |
254 | 175.4 | 175.2 | 153.1 |
255 | 175.4 | 175.3 | 154.6 |
256 | 175.3 | 175.1 | 154.4 |
257 | 175.2 | 175.2 | 154 |
258 | 175.2 | 175 | 151.8 |
259 | 174.7 | 174.7 | 152 |
260 | 175 | 175.1 | 153 |
261 | 175.4 | 175.3 | 153.9 |
261 | 175.4 | 175.3 | 153.9 |
262 | 175.4 | 175.2 | 153.5 |
263 | 175.3 | 175.2 | 153.9 |
264 | 175.3 | 175.1 | 153.8 |
265 | 175.2 | 175.1 | 153.8 |
266 | 175.2 | 175.1 | 153 |
267 | 175.2 | 175 | 153.3 |
268 | 175.1 | 174.9 | 152.8 |
269 | 174.7 | 174.4 | 150.6 |
270 | 174.4 | 174.3 | 149.4 |
271 | 174.5 | 174.5 | 150.5 |
272 | 174.3 | 174.2 | 150.7 |
273 | 174.4 | 174.2 | 150 |
274 | 174.5 | 174.3 | 149.6 |
275 | 174 | 174 | 148.1 |
276 | 174.1 | 174 | 149.6 |
277 | 174 | 173.9 | 149 |
278 | 173.9 | 173.8 | 148 |
279 | 173.9 | 173.7 | 148 |
280 | 173.8 | 173.8 | 149 |
281 | 173.8 | 173.7 | 147 |
282 | 173.7 | 173.1 | 145.7 |
283 | 173.4 | 173.4 | 146 |
284 | 173.5 | 173.3 | 145.7 |
285 | 173.3 | 173.2 | 145.7 |
286 | 173 | 172.8 | 142.1 |
287 | 172.9 | 172.8 | 142.7 |
288 | 172.9 | 172.7 | 142.4 |
289 | 172.7 | 172.6 | 141.4 |
290 | 172.7 | 172.7 | 143 |
291 | 173 | 173.2 | 147 |
292 | 173.9 | 173.8 | 148.5 |
293 | 173.7 | 173.3 | 145.2 |
294 | 173.8 | 173.9 | 153 |
295 | 174.1 | 174 | 153 |
296 | 174.2 | 174.2 | 153.3 |
297 | 174 | 173.8 | 152.1 |
298 | 173.9 | 173.8 | 152.1 |
299 | 173.7 | 173.6 | 151.9 |
300 | 173.9 | 173.9 | 153.6 |
301 | 174 | 173.8 | 152.8 |
302 | 174.1 | 173.8 | 152.8 |
303 | 173.8 | 173.8 | 152.8 |
304 | 173.8 | 173.8 | 152.4 |
305 | 174 | 174 | 153.2 |
306 | 174 | 173.8 | 152.3 |
307 | 173.9 | 173.8 | 152.4 |
308 | 173.9 | 173.9 | 152.8 |
309 | 173.9 | 173.7 | 152.3 |
310 | 173.8 | 173.6 | 152 |
311 | 173.7 | 173.8 | 152.4 |
312 | 174 | 173.8 | 153 |
313 | 173.9 | 173.8 | 153.6 |
314 | 174 | 173.8 | 153.8 |
315 | 174 | 173.9 | 154.3 |
316 | 174 | 174 | 154 |
317 | 174.1 | 174 | 154 |
318 | 173.8 | 173.5 | 152.5 |
319 | 173.7 | 173.7 | 153 |
320 | 173.6 | 173.5 | 152.7 |
321 | 173.6 | 173.5 | 152.1 |
322 | 173.6 | 173.6 | 153.1 |
323 | 173.8 | 170.9 | 154.1 |
324 | 178.5 | 174.9 | 155 |
325 | 175.2 | 174.8 | 153.9 |
326 | 174.7 | 174.5 | 154.3 |
327 | 174.6 | 174.2 | 153 |
328 | 174.3 | 174.1 | 153.3 |
329 | 174.1 | 174 | 152.8 |
330 | 174 | 173.8 | 152.6 |
331 | 173.9 | 173.6 | 152.6 |
332 | 173.9 | 173.6 | 151.9 |
333 | 166.1 | 173.5 | 152.1 |
334 | 173.6 | 173.5 | 151.3 |
335 | 173.7 | 173.5 | 152.6 |
336 | 173.8 | 173.6 | 153.2 |
337 | 173.6 | 173.5 | 152.8 |
338 | 173.5 | 173.5 | 152.6 |
339 | 173.5 | 173.3 | 152.6 |
339 | 173.5 | 173.3 | 152.6 |
340 | 173.4 | 173.2 | 151.7 |
341 | 173.2 | 173.2 | 151.6 |
342 | 173.1 | 172.9 | 149.8 |
343 | 173.1 | 173.2 | 151.9 |
344 | 173.3 | 173.1 | 152.6 |
345 | 173.4 | 173.5 | 153.8 |
346 | 173.8 | 173.6 | 154.3 |
347 | 173.8 | 173.6 | 154.2 |
348 | 173.6 | 173.5 | 153.4 |
349 | 173.5 | 173.1 | 152.7 |
350 | 173.2 | 173.1 | 152.7 |
351 | 173.3 | 173.2 | 152.4 |
352 | 173.2 | 173 | 152.2 |
353 | 173 | 172.9 | 151.7 |
354 | 172.8 | 172.4 | 149.2 |
355 | 172.5 | 172.6 | 150.8 |
356 | 172.7 | 172.5 | 150.8 |
357 | 172.3 | 172.3 | 150.5 |
358 | 172.5 | 172.4 | 151.3 |
359 | 172.5 | 172.4 | 151 |
360 | 172.4 | 172.2 | 150.6 |
361 | 172.1 | 172.1 | 149.9 |
362 | 172.4 | 172.2 | 149.5 |
363 | 172.1 | 172.1 | 149.2 |
364 | 172 | 172 | 149 |
365 | 172.2 | 172.1 | 149.6 |
366 | 172.2 | 172.1 | 149.6 |
367 | 172.2 | 172.2 | 150.3 |
368 | 172.3 | 172.2 | 150.1 |
369 | 172.3 | 172.2 | 150.4 |
370 | 172.2 | 172.2 | 150.1 |
371 | 172.2 | 172 | 150.2 |
372 | 172.1 | 172.1 | 150.2 |
373 | 172.1 | 172 | 150 |
374 | 172 | 171.9 | 149.5 |
375 | 171.9 | 171.8 | 149.4 |
376 | 172 | 171.9 | 150 |
377 | 172.1 | 172 | 150.7 |
378 | 172 | 172 | 150.7 |
379 | 172.3 | 172.2 | 151.5 |
380 | 172.2 | 172 | 151.2 |
381 | 172.1 | 172 | 150.8 |
382 | 172 | 172 | 151.1 |
383 | 172.1 | 171.8 | 150.6 |
384 | 171.9 | 171.9 | 149.8 |
385 | 171.9 | 171.7 | 150.5 |
386 | 171.8 | 171.8 | 151.1 |
387 | 172 | 172 | 151.7 |
388 | 172.1 | 172.1 | 151.9 |
389 | 172.4 | 172.3 | 152.7 |
390 | 172.5 | 172.4 | 152.7 |
391 | 172.3 | 172 | 151.2 |
392 | 172 | 171.9 | 150.9 |
393 | 171.8 | 171.6 | 149.8 |
394 | 171.6 | 171.6 | 149.5 |
395 | 171.5 | 171.3 | 148.3 |
396 | 171.4 | 171.4 | 149.8 |
397 | 171.7 | 171.7 | 151.2 |
398 | 171.8 | 171.9 | 151.3 |
399 | 172.1 | 172 | 152.4 |
400 | 172.2 | 172.1 | 152.6 |
401 | 172.1 | 171.9 | 152.1 |
402 | 171.9 | 171.8 | 151.2 |
403 | 171.7 | 171.6 | 151.2 |
404 | 171.8 | 171.7 | 151.2 |
405 | 171.7 | 171.6 | 151.2 |
406 | 171.7 | 171.6 | 150.9 |
407 | 171.7 | 171.7 | 151.3 |
408 | 171.8 | 171.8 | 151.8 |
409 | 172.3 | 171.7 | 151.4 |
410 | 171.8 | 171.8 | 151.8 |
411 | 171.8 | 171.7 | 151.7 |
412 | 171.7 | 171.5 | 150.8 |
413 | 171.2 | 171 | 148.2 |
414 | 170.7 | 170.6 | 146.8 |
415 | 170.4 | 170.3 | 145.1 |
416 | 170.1 | 170 | 143.7 |
417 | 170 | 170 | 145.1 |
418 | 170.8 | 171.1 | 149.6 |
419 | 171.4 | 171.3 | 150 |
420 | 171.3 | 171.3 | 151.3 |
421 | 171.5 | 171.5 | 151.6 |
422 | 171.5 | 171.5 | 151.3 |
423 | 171.5 | 171 | 150.1 |
424 | 171.1 | 171 | 149.7 |
424 | 171.1 | 171 | 149.7 |
425 | 171 | 170.9 | 148.4 |
426 | 170.8 | 170.4 | 147.8 |
427 | 170.6 | 170.5 | 147.6 |
428 | 170.4 | 170.5 | 148.3 |
429 | 170.7 | 170.6 | 148.2 |
430 | 170.9 | 170.8 | 149 |
431 | 170.8 | 170.5 | 148.2 |
432 | 170.3 | 170.3 | 117.1 |
433 | 170.6 | 170.4 | 117.8 |
434 | 170.3 | 170.1 | 146.1 |
435 | 170 | 169.8 | 145 |
436 | 170.2 | 170.4 | 147.9 |
437 | 170.5 | 170.4 | 148 |
438 | 170.4 | 170.3 | 147.4 |
439 | 170.6 | 170.5 | 147.9 |
440 | 170.5 | 170.3 | 147.7 |
441 | 170.5 | 170.4 | 148.4 |
442 | 170.5 | 170.3 | 148.3 |
443 | 170.5 | 170.4 | 148.8 |
444 | 170.5 | 170.4 | 148.3 |
445 | 170.4 | 170.3 | 147.7 |
446 | 170.3 | 170.2 | 148.1 |
447 | 170.2 | 170.2 | 147.7 |
448 | 170.2 | 170.1 | 147.3 |
449 | 170.1 | 169.9 | 145.4 |
450 | 170 | 170.1 | 147.8 |
451 | 170.5 | 170.4 | 148.4 |
452 | 170.4 | 170.3 | 148.7 |
453 | 170.5 | 170.2 | 148.1 |
454 | 170.3 | 170.3 | 148.8 |
455 | 170.4 | 170.3 | 148.3 |
456 | 170.4 | 170.3 | 149 |
457 | 170.3 | 170.3 | 148.4 |
458 | 170.3 | 170.1 | 148 |
459 | 170.2 | 170.1 | 148 |
460 | 170.1 | 170 | 148.2 |
461 | 170 | 169.8 | 146 |
462 | 169.8 | 169.7 | 146.6 |
463 | 169.6 | 169.2 | 143.8 |
464 | 169 | 169 | 143.7 |
465 | 169.5 | 169.7 | 146.5 |
466 | 169.6 | 169.6 | 146.6 |
467 | 169.7 | 169.6 | 146.3 |
468 | 169.7 | 169.6 | 146.7 |
469 | 169.7 | 169.5 | 146.7 |
470 | 169.5 | 169.5 | 146 |
471 | 169.6 | 169.5 | 145.6 |
472 | 169.5 | 169.3 | 145.3 |
473 | 169.3 | 169.3 | 145.4 |
474 | 169.3 | 169.1 | 144.7 |
475 | 169.2 | 169.1 | 144.6 |
476 | 169.1 | 169.1 | 144.4 |
477 | 169 | 168.8 | 143.6 |
478 | 168.8 | 168.7 | 142.9 |
479 | 168.6 | 168.5 | 142 |
480 | 168.5 | 168.3 | 140.6 |
481 | 168.2 | 168.1 | 140.3 |
482 | 168.3 | 168.3 | 142.1 |
483 | 168.4 | 168.2 | 141 |
484 | 168 | 168.2 | 140 |
485 | 168 | 168 | 142.5 |
486 | 168.3 | 168.5 | 142.5 |
487 | 168.8 | 168.7 | 143.5 |
488 | 168.9 | 168.8 | 144 |
489 | 168.9 | 168.8 | 144.6 |
490 | 168.9 | 168.8 | 144.4 |
491 | 168.8 | 168.8 | 144 |
492 | 168.8 | 168.7 | 143.7 |
493 | 169 | 169 | 146 |
494 | 169.2 | 169 | 145.9 |
495 | 168.6 | 168.4 | 141.8 |
496 | 168.3 | 168.3 | 144 |
497 | 168.8 | 169 | 146 |
498 | 169.2 | 169 | 146.6 |
499 | 169.1 | 169 | 146.2 |
500 | 169 | 168.9 | 146 |
501 | 168.9 | 168.9 | 145.4 |
502 | 168.9 | 168.7 | 145.1 |
503 | 168.6 | 168.6 | 144.4 |
504 | 168.8 | 168.8 | 145.2 |
505 | 169.1 | 169.1 | 147.5 |
506 | 168.8 | 168.3 | 143.2 |
507 | 168.1 | 167.9 | 143 |
508 | 168.1 | 168.5 | 146.2 |
509 | 169.3 | 169.2 | 147.7 |
510 | 169.3 | 169.2 | 148 |
511 | 169.3 | 169.2 | 147.8 |
512 | 169.2 | 169.1 | 146.7 |
513 | 169.1 | 169 | 146.2 |
514 | 169 | 169 | 147.2 |
515 | 169.3 | 169.3 | 148.3 |
516 | 169.5 | 169.3 | 148.6 |
517 | 169.3 | 169.2 | 148.2 |
518 | 169.3 | 169.1 | 148.2 |
519 | 169.3 | 169.3 | 148.7 |
520 | 169.6 | 169.5 | 148.9 |
521 | 169.5 | 169.3 | 149.1 |
522 | 169.3 | 169.3 | 148.6 |
523 | 169.3 | 169.1 | 148.2 |
524 | 169.1 | 169 | 148.1 |
525 | 169.1 | 169 | 148 |
526 | 169.3 | 169.3 | 148.5 |
527 | 169.4 | 169.2 | 148.1 |
528 | 169.2 | 169.1 | 148.4 |
529 | 169.3 | 169.3 | 148.5 |
530 | 169.3 | 169.1 | 148.7 |
531 | 169.2 | 169.2 | 148.5 |
531 | 169.2 | 169.2 | 148.5 |
532 | 169.2 | 169.2 | 148.1 |
533 | 169.2 | 169 | 147.9 |
534 | 169 | 169 | 148.1 |
535 | 169.1 | 169 | 147.7 |
536 | 169 | 168.8 | 148 |
537 | 168.9 | 168.7 | 146.1 |
538 | 168.5 | 168.2 | 145.1 |
539 | 168.4 | 168 | 145 |
540 | 168 | 167.9 | 145.1 |
541 | 168.1 | 168.1 | 145.2 |
542 | 168.1 | 168 | 143.7 |
543 | 168.2 | 168.2 | 145.7 |
544 | 168.2 | 168.2 | 145.3 |
545 | 168.3 | 168.1 | 145.3 |
546 | 168.1 | 167.9 | 144.8 |
547 | 167.8 | 167.8 | 144 |
548 | 167.9 | 167.9 | 144.5 |
549 | 168.1 | 168 | 144.4 |
550 | 168.1 | 167.9 | 145.4 |
551 | 168.1 | 168.1 | 146.1 |
552 | 168.1 | 168 | 146.6 |
553 | 168.2 | 168 | 145.7 |
554 | 167.6 | 167.2 | 142 |
555 | 167.2 | 167.1 | 141.4 |
556 | 167 | 166.9 | 140 |
557 | 166.8 | 166.7 | 138.9 |
558 | 166.7 | 166.7 | 140.1 |
559 | 167.2 | 166.9 | 138.8 |
560 | 166.7 | 166.8 | 138.8 |
561 | 167 | 166.8 | 133.9 |
562 | 166.5 | 166.4 | 134.7 |
563 | 167.4 | 167.5 | 137.7 |
564 | 167.4 | 167.2 | 135.4 |
565 | 166.9 | 166.9 | 134.7 |
566 | 167.1 | 167.1 | 134.5 |
567 | 167.2 | 167.1 | 133.2 |
568 | 167.5 | 167.3 | 141 |
569 | 167 | 166.9 | 140.1 |
570 | 166.9 | 166.7 | 139.7 |
571 | 167 | 166.7 | 139.6 |
572 | 166.7 | 167.1 | 141.9 |
573 | 167.2 | 161.2 | 133.8 |
574 | 167.1 | 167.2 | 141.9 |
575 | 167.3 | 167.3 | 142.2 |
576 | 167.3 | 167.2 | 141.3 |
577 | 167.2 | 167.1 | 140.8 |
578 | 167.1 | 166.8 | 139 |
579 | 166.7 | 166.5 | 137.8 |
580 | 166.4 | 166.3 | 137.4 |
581 | 166.4 | 166.8 | 143.6 |
582 | 167.5 | 167.1 | 141.6 |
583 | 167.1 | 167.2 | 142.4 |
584 | 167.1 | 167.1 | 142.2 |
585 | 167.3 | 167.3 | 142 |
586 | 167.3 | 167.1 | 141.7 |
587 | 167.1 | 166.8 | 140.6 |
588 | 167.1 | 167.3 | 142.8 |
589 | 167.5 | 167.5 | 143.8 |
590 | 167.4 | 167.2 | 142.8 |
591 | 167.3 | 167.1 | 140.7 |
592 | 167.1 | 166.8 | 138.7 |
593 | 166.2 | 166 | 136.4 |
594 | 166.3 | 166.4 | 139.3 |
595 | 166.6 | 166.6 | 140.3 |
596 | 166.8 | 166.8 | 141.4 |
597 | 167.1 | 167 | 141.8 |
598 | 167.1 | 166.9 | 138.9 |
599 | 166.9 | 166.9 | 141.4 |
600 | 167 | 167 | 141.8 |
601 | 167.1 | 167 | 142.7 |
602 | 166.9 | 166.8 | 141.2 |
603 | 166.8 | 166.8 | 140.8 |
604 | 166.9 | 166.6 | 140.2 |
605 | 166.6 | 166.6 | 140.2 |
606 | 166.2 | 166.2 | 136.9 |
607 | 167.1 | 167.3 | 141.8 |
608 | 167.3 | 167 | 140.8 |
609 | 167.2 | 167 | 142.1 |
610 | 167.1 | 167 | 141.9 |
611 | 167 | 166.9 | 140.8 |
612 | 167 | 166.8 | 140.7 |
613 | 166.9 | 166.7 | 140.9 |
614 | 167 | 166.9 | 141.2 |
615 | 166.7 | 166.3 | 138.8 |
616 | 166.1 | 165.8 | 137.1 |
617 | 165.9 | 166 | 137.2 |
618 | 166 | 166.2 | 140.1 |
619 | 166.7 | 166.9 | 141.4 |
620 | 166.8 | 166.7 | 141.6 |
621 | 166.8 | 166.7 | 141 |
622 | 159.3 | 166 | 139.3 |
623 | 165.6 | 165.7 | 137.7 |
624 | 165.4 | 165.6 | 137.8 |
625 | 165.5 | 165.5 | 136.3 |
626 | 165.6 | 165.8 | 138.8 |
627 | 166.2 | 166.1 | 139.2 |
628 | 166.1 | 165.8 | 136.9 |
629 | 165.6 | 165.5 | 135.7 |
630 | 164.3 | 165.3 | 135.4 |
631 | 164 | 164.7 | 135.8 |
632 | 164.8 | 165 | 136.5 |
633 | 165 | 165.1 | 135.7 |
634 | 165.2 | 165.1 | 135.5 |
635 | 165 | 165 | 134 |
636 | 165 | 165 | 134.3 |
637 | 165 | 165 | 134.1 |
638 | 165 | 164.8 | 134.1 |
639 | 165.2 | 165.3 | 136 |
640 | 165.1 | 164.5 | 133 |
641 | 164.3 | 164.3 | 133 |
642 | 164.9 | 164.7 | 135.3 |
643 | 165.1 | 165.2 | 136.3 |
644 | 164.9 | 164.7 | 134.2 |
645 | 164.6 | 164.6 | 135.3 |
646 | 165 | 165 | 136.1 |
647 | 165.1 | 165 | 136.1 |
648 | 165 | 165 | 135.8 |
649 | 164.9 | 164.8 | 135.4 |
649 | 164.9 | 164.8 | 135.4 |
650 | 165 | 164.8 | 135.9 |
651 | 164.9 | 164.9 | 136.2 |
652 | 165 | 164.8 | 135.8 |
653 | 165 | 165 | 135.7 |
654 | 165 | 164.8 | 135.6 |
655 | 164.9 | 164.8 | 135.9 |
656 | 164.8 | 164.8 | 135.4 |
657 | 164.8 | 164.6 | 134.8 |
658 | 162.1 | 164.8 | 136 |
659 | 164.9 | 165 | 137.1 |
660 | 165.2 | 165.1 | 136.3 |
661 | 165.2 | 165.2 | 138.1 |
662 | 165.5 | 165.5 | 138.6 |
663 | 165.4 | 164.8 | 134.2 |
664 | 164.8 | 164.9 | 136.9 |
665 | 165.1 | 165.2 | 137.5 |
666 | 165.1 | 164.9 | 136.8 |
667 | 164.9 | 164.7 | 135.9 |
668 | 164.8 | 164.5 | 134.4 |
669 | 164 | 164.1 | 134.5 |
670 | 164.2 | 163.6 | 131.4 |
671 | 164.2 | 164.5 | 136.4 |
672 | 164.8 | 164.9 | 135.8 |
673 | 164.9 | 164.7 | 136.2 |
674 | 164.7 | 164.6 | 136.2 |
675 | 164.5 | 164.3 | 134.3 |
676 | 164.2 | 164.2 | 133.1 |
677 | 164.3 | 164.5 | 136.1 |
678 | 164.4 | 163.8 | 132.4 |
679 | 163.8 | 163.8 | 132.5 |
680 | 163.9 | 163.8 | 132.3 |
681 | 164.2 | 164.4 | 135.9 |
682 | 164.6 | 164.7 | 136.2 |
683 | 164.8 | 164.7 | 136.6 |
684 | 164.7 | 164.7 | 136.2 |
685 | 164.8 | 164.7 | 135.9 |
686 | 164.7 | 164.5 | 135.9 |
687 | 164.5 | 164.4 | 135.3 |
688 | 164.2 | 164.4 | 134.5 |
689 | 163.9 | 155.8 | 126.6 |
690 | 163.9 | 164.4 | 136.8 |
691 | 164.5 | 164.6 | 137.7 |
692 | 164.5 | 164.6 | 136.3 |
693 | 164.6 | 164.5 | 136.2 |
694 | 164.5 | 164.4 | 135.8 |
695 | 164.8 | 164.6 | 136.6 |
696 | 164.2 | 163.9 | 134.2 |
697 | 163.7 | 163.4 | 132.6 |
698 | 163.5 | 163.4 | 132.8 |
699 | 164.1 | 164.4 | 136.7 |
700 | 164.7 | 164.7 | 137.4 |
701 | 164.8 | 164.7 | 137.7 |
702 | 164.7 | 164.6 | 137.6 |
703 | 164.6 | 164.6 | 137.3 |
704 | 164.6 | 164.4 | 136.2 |
705 | 164.2 | 163.7 | 133.8 |
706 | 163.5 | 163.1 | 131.3 |
707 | 163 | 162.8 | 130.3 |
708 | 162.8 | 163.4 | 133.2 |
709 | 164 | 163.9 | 134.7 |
710 | 164 | 163.9 | 134.5 |
711 | 163.9 | 163.9 | 134.4 |
712 | 163.9 | 163.9 | 134.4 |
713 | 163.8 | 163.6 | 133.4 |
714 | 163.7 | 163.7 | 133.9 |
715 | 163.8 | 163.7 | 133.7 |
716 | 163.7 | 163.6 | 133 |
717 | 163.6 | 163.6 | 133.1 |
718 | 163.6 | 163.6 | 133 |
719 | 163.6 | 163.4 | 133.2 |
720 | 163.4 | 163.4 | 133.3 |
721 | 163.5 | 163.3 | 132.8 |
722 | 163.3 | 163.3 | 131.5 |
723 | 163.3 | 163.2 | 131.2 |
724 | 163.2 | 163 | 131.2 |
725 | 163.1 | 163 | 130.8 |
726 | 163 | 162.9 | 130.3 |
727 | 162.9 | 162.9 | 130 |
728 | 162.9 | 162.7 | 129.6 |
729 | 162.7 | 162.8 | 129.6 |
730 | 162.8 | 162.7 | 129.6 |
731 | 162.8 | 162.6 | 129.6 |
732 | 162.6 | 162.6 | 129.4 |
733 | 162.6 | 162.4 | 128.2 |
734 | 162.4 | 162.4 | 128.2 |
735 | 164.6 | 164.3 | 129.7 |
736 | 164.3 | 164.2 | 130 |
737 | 164.3 | 164.4 | 131.3 |
738 | 164.5 | 164.4 | 131.7 |
739 | 164.4 | 164.3 | 130.6 |
740 | 164.1 | 164 | 129.7 |
741 | 164 | 163.9 | 129.3 |
742 | 163.9 | 163.7 | 128.7 |
743 | 163.8 | 164 | 130.5 |
744 | 164.1 | 163.9 | 129.5 |
745 | 163.7 | 163.7 | 129.7 |
746 | 163.5 | 163.3 | 127.5 |
747 | 163.8 | 164.1 | 132.3 |
748 | 164.3 | 164.3 | 132.8 |
749 | 164.5 | 164.5 | 133.5 |
750 | 164.5 | 164.5 | 132.7 |
751 | 164.5 | 164.4 | 133.3 |
752 | 164.4 | 164.4 | 132.9 |
753 | 164.4 | 164.2 | 132.7 |
754 | 164.2 | 163.9 | 130.8 |
755 | 163.9 | 164.1 | 132.9 |
756 | 164.4 | 164.5 | 134.7 |
757 | 164.5 | 164.2 | 131.5 |
758 | 164.3 | 164.4 | 134.6 |
759 | 163.7 | 163.3 | 128 |
760 | 163.3 | 163.5 | 128.6 |
761 | 163.6 | 163.6 | 130.1 |
762 | 163.6 | 163.4 | 129.6 |
763 | 163.3 | 163.3 | 129.4 |
764 | 163.6 | 163.9 | 132.5 |
765 | 163.7 | 163.5 | 129.9 |
766 | 163.5 | 163.8 | 131.4 |
767 | 163.5 | 163.5 | 131.4 |
768 | 164.2 | 164.3 | 133 |
769 | 164.2 | 164.1 | 132.8 |
770 | 164.1 | 164.1 | 133.7 |
771 | 164 | 164.1 | 133 |
772 | 164.1 | 164.2 | 133 |
773 | 164.1 | 164 | 133.1 |
774 | 163.9 | 163.9 | 132.9 |
775 | 163.8 | 163.8 | 133.1 |
776 | 164.3 | 164.2 | 134.5 |
777 | 164.2 | 164 | 131.6 |
778 | 163.6 | 163.7 | 133.3 |
779 | 164.1 | 164.1 | 133.3 |
780 | 164.1 | 164 | 133.1 |
781 | 164 | 163.9 | 133 |
782 | 164 | 164 | 132.9 |
783 | 164 | 163.9 | 133.1 |
784 | 163.9 | 163.9 | 132.7 |
785 | 164 | 163.9 | 133.1 |
786 | 164 | 164 | 134.3 |
787 | 163.8 | 163.7 | 133.8 |
788 | 163.9 | 163.8 | 132 |
789 | 163.6 | 163.7 | 133.1 |
790 | 163.9 | 163.9 | 133.8 |
791 | 164 | 164.2 | 134.4 |
792 | 164.2 | 163.9 | 133.6 |
793 | 163.8 | 157.3 | 132.9 |
794 | 164.7 | 163.8 | 132.7 |
795 | 164.1 | 164.1 | 134.6 |
796 | 164.3 | 164.2 | 134.4 |
797 | 164.3 | 164.2 | 135 |
798 | 164.2 | 164.3 | 135.2 |
799 | 164.4 | 164.4 | 135.1 |
799 | 164.4 | 164.4 | 135.1 |
800 | 164.4 | 164.1 | 133.2 |
801 | 164.2 | 164.2 | 135.6 |
802 | 164.2 | 164.2 | 134.7 |
2)常规电解液与天然石墨负极匹配整体电池循环数据:
整体电池为铝塑膜电池,标称容量180mA·h;正极为钴酸锂,负极为天然石墨,电解液体系为常规电解液;
首次1C倍率放电容量为187mA·h;1C倍率190次循环后放电容量为124mA·h;容量保持率为66%;
循环序号 | 充电/mA·h | 放电/mA·h | 平台容量/mA·h |
1 | 216.3 | 192 | 181 |
2 | 190.1 | 187 | 148.2 |
3 | 187.8 | 186.4 | 149.6 |
4 | 186.7 | 185.5 | 147.9 |
5 | 186.7 | 185.8 | 151.3 |
6 | 186.9 | 185.9 | 153.3 |
7 | 186.5 | 185.7 | 153.5 |
8 | 186.2 | 185.5 | 154.1 |
9 | 186 | 185.4 | 153.8 |
10 | 185.9 | 185.1 | 153.3 |
11 | 185.5 | 184.8 | 152.7 |
12 | 185.2 | 184.7 | 151.8 |
13 | 185.1 | 184.5 | 152.2 |
14 | 185.3 | 184.8 | 154.2 |
15 | 185.2 | 184.5 | 153.2 |
16 | 184.9 | 184.3 | 153.4 |
17 | 185 | 184.5 | 154.6 |
18 | 184.9 | 184.4 | 154.1 |
19 | 184.8 | 184.4 | 153.6 |
20 | 184.6 | 184 | 152.7 |
21 | 184.4 | 183.8 | 151.9 |
22 | 184 | 183.5 | 150.6 |
23 | 183.6 | 183.1 | 148.7 |
24 | 183.8 | 183.4 | 151.2 |
25 | 183.7 | 183.2 | 150.3 |
26 | 183.7 | 183 | 150.2 |
27 | 183.3 | 183 | 149.6 |
28 | 183.3 | 182.9 | 149.2 |
29 | 183.3 | 182.9 | 148.2 |
30 | 183.2 | 182.7 | 147.1 |
31 | 182.9 | 182.4 | 145.2 |
32 | 182.6 | 182.3 | 145.9 |
33 | 183.1 | 182.6 | 149.6 |
34 | 183.2 | 182.7 | 150.1 |
35 | 183.2 | 182.7 | 150.6 |
36 | 183.4 | 182.9 | 150.9 |
37 | 183.2 | 182.7 | 149 |
38 | 183 | 182.4 | 146.8 |
39 | 182.4 | 181.9 | 145.6 |
40 | 182.3 | 181.8 | 144.9 |
41 | 182.1 | 181.6 | 143.3 |
42 | 181.9 | 181.3 | 141.9 |
43 | 181.6 | 181.2 | 142.3 |
44 | 181.9 | 181.4 | 143.4 |
45 | 181.6 | 181.1 | 141.3 |
46 | 181.4 | 180.9 | 141.6 |
47 | 181.4 | 180.8 | 140.6 |
48 | 181 | 180.2 | 137.3 |
49 | 180.1 | 179.6 | 134.9 |
50 | 180 | 179.6 | 135.2 |
51 | 180.1 | 179.5 | 134 |
52 | 179.8 | 179.4 | 133 |
53 | 179.8 | 179.2 | 134.3 |
54 | 179.3 | 178.6 | 130.4 |
55 | 178.8 | 178.4 | 129.9 |
56 | 178.7 | 178.3 | 129.6 |
57 | 178.6 | 178.1 | 128.4 |
58 | 178.2 | 177.5 | 125.9 |
59 | 177.4 | 177.1 | 124.3 |
60 | 177.5 | 177 | 123.4 |
61 | 177.1 | 176.5 | 120.8 |
62 | 176.6 | 176 | 118.4 |
63 | 176.2 | 175.8 | 118.8 |
64 | 176.2 | 175.5 | 118 |
65 | 175.7 | 175.2 | 116.3 |
66 | 175.4 | 174.9 | 115.6 |
67 | 175.1 | 174.8 | 114.7 |
68 | 174.9 | 174.4 | 114.4 |
69 | 174.6 | 174.1 | 113.2 |
70 | 174.2 | 173.8 | 111.7 |
71 | 173.9 | 173.3 | 110.2 |
72 | 173.4 | 172.8 | 108.1 |
73 | 172.9 | 172.5 | 107.6 |
74 | 172.8 | 172.2 | 107.1 |
75 | 172.3 | 171.8 | 105.6 |
76 | 171.9 | 171.4 | 104.1 |
77 | 171.4 | 170.5 | 101.2 |
78 | 170 | 169.5 | 97 |
79 | 170.1 | 169.8 | 99.7 |
80 | 169.8 | 169.3 | 97.6 |
81 | 169.3 | 168.7 | 95.5 |
82 | 168.5 | 167.9 | 93.6 |
83 | 168 | 167.4 | 92 |
84 | 167.6 | 167.2 | 92.2 |
85 | 167.6 | 167.2 | 92.3 |
86 | 167.4 | 167.1 | 91.2 |
87 | 167 | 166.4 | 89.5 |
88 | 166.4 | 165.7 | 88.1 |
89 | 165.5 | 164.9 | 85.6 |
90 | 164.9 | 164.6 | 84.7 |
91 | 164.6 | 163.9 | 83.1 |
92 | 163.7 | 162.9 | 80.5 |
93 | 162.9 | 162.6 | 79.6 |
94 | 162.6 | 161.9 | 77.8 |
95 | 161.9 | 161.6 | 78.7 |
96 | 161.9 | 161.3 | 77.3 |
97 | 161.3 | 161.1 | 76.1 |
98 | 161.1 | 160.2 | 75 |
99 | 160.3 | 159.9 | 73.8 |
100 | 159.8 | 159.1 | 71.9 |
101 | 158.9 | 158.2 | 70.2 |
102 | 158 | 157.1 | 68.1 |
103 | 157.3 | 157.2 | 68.1 |
104 | 157.7 | 157.4 | 69 |
105 | 157 | 156.5 | 66.3 |
106 | 157 | 156.5 | 66.4 |
107 | 156.4 | 156.1 | 65.7 |
108 | 155.8 | 155 | 63.8 |
109 | 155.1 | 154.5 | 62.5 |
110 | 154.2 | 153.6 | 60.9 |
111 | 153.5 | 152.8 | 59.7 |
112 | 152.4 | 151.8 | 57.9 |
113 | 151.6 | 150.5 | 56.6 |
114 | 149.5 | 148.7 | 53 |
115 | 148.7 | 148.1 | 52.3 |
116 | 148.1 | 147.8 | 51.8 |
117 | 148 | 148.1 | 52.1 |
118 | 148.1 | 147.4 | 50.9 |
119 | 146.4 | 145.3 | 47.7 |
120 | 146.3 | 146.4 | 49.6 |
121 | 146.3 | 145.5 | 48.4 |
122 | 145.2 | 144.3 | 47 |
123 | 144 | 142.6 | 45.7 |
124 | 141.1 | 139.2 | 41.3 |
125 | 138.7 | 138 | 40.1 |
126 | 137.9 | 137.1 | 39.4 |
127 | 136.4 | 135.9 | 37.8 |
128 | 135.3 | 133.1 | 35.6 |
129 | 132 | 131.4 | 33.8 |
130 | 131.1 | 131 | 33.3 |
131 | 130.8 | 129.6 | 32.5 |
132 | 128.2 | 126.4 | 30.1 |
133 | 129.3 | 131.7 | 33.4 |
134 | 132.7 | 133.7 | 35 |
135 | 133.7 | 132.6 | 34 |
136 | 132.6 | 132.5 | 33.6 |
136 | 132.6 | 132.5 | 33.6 |
137 | 132.8 | 132.8 | 33.6 |
138 | 132.2 | 130.1 | 31.8 |
139 | 128.2 | 125.7 | 28.7 |
140 | 123.5 | 120.7 | 25.7 |
141 | 118.6 | 116.6 | 23.1 |
142 | 114.6 | 112.8 | 21.1 |
143 | 116.8 | 121.6 | 25.1 |
144 | 124.4 | 126.8 | 28.6 |
145 | 127 | 126.2 | 27.7 |
146 | 126.8 | 127 | 27.8 |
147 | 127.1 | 126.5 | 27.4 |
148 | 124.5 | 121.9 | 25 |
149 | 119.7 | 117.1 | 21.8 |
150 | 116.1 | 114.8 | 21 |
151 | 113 | 111 | 19.4 |
152 | 109.9 | 109.1 | 18.4 |
153 | 108.9 | 109.3 | 18.3 |
154 | 108.7 | 107.8 | 17.8 |
155 | 108.4 | 107.7 | 17.6 |
156 | 108 | 109.7 | 18.1 |
157 | 110.9 | 110.1 | 18.3 |
158 | 109.6 | 108.8 | 17.4 |
159 | 108.4 | 107.9 | 17 |
160 | 107.5 | 106.7 | 16.5 |
161 | 106.4 | 105.4 | 15.9 |
162 | 104.6 | 103.5 | 15.2 |
163 | 107.2 | 110.7 | 17.2 |
164 | 112.2 | 112.3 | 17.8 |
165 | 111.8 | 110.6 | 17 |
166 | 111 | 111.5 | 17.1 |
167 | 113.3 | 114.1 | 18.2 |
168 | 114.7 | 114.3 | 18 |
169 | 114.9 | 115.1 | 18.2 |
170 | 115.4 | 114.5 | 18 |
171 | 114.2 | 113.2 | 17.3 |
172 | 112.4 | 111.2 | 16.5 |
173 | 113.3 | 115.8 | 18.2 |
174 | 120.5 | 123.4 | 21.2 |
175 | 128.2 | 130.5 | 24.8 |
176 | 131.6 | 134.2 | 27.7 |
177 | 132 | 128.8 | 24.4 |
178 | 127.3 | 125.5 | 22.7 |
179 | 125 | 124.3 | 21.7 |
180 | 122.4 | 120.7 | 20.1 |
181 | 119.2 | 117.4 | 18.7 |
182 | 117.1 | 118.2 | 18.5 |
183 | 122.3 | 124.2 | 21.5 |
184 | 126.1 | 127 | 22.6 |
185 | 129.4 | 129.4 | 25 |
186 | 129.4 | 128.8 | 23.8 |
187 | 127.2 | 126.4 | 22.4 |
188 | 117.7 | 116.7 | 19.9 |
189 | 124.6 | 125.8 | 21.9 |
190 | 125 | 123.6 | 20.9 |
Claims (6)
1、一种匹配锂离子二次电池天然石墨负极的电解液,含有有机溶剂和锂盐电解质,其特征在于所述电解液还含有含硼元素化合物的添加剂。
2、如权利要求1所述的匹配锂离子二次电池天然石墨负极的电解液,其特征在于,所述的含硼元素化合物的化学式为:AxbyCzDw:其中
A元素为碱金属,x值范围为0≤x≤4;
B元素为硼元素,y值范围为0≤y≤4;
C元素为:C,Si,Ge,Sn,N,P,As,S,Se之其中一种,z值范围为0≤z≤8;
D元素为:N,O,S,F,Cl,Br之其中一种,w值范围为:0≤w≤32。
3、如权利要求2所述的匹配锂离子二次电池天然石墨负极的电解液,其特征在于,所述的A元素为Li,Na,K,Ru,Se,Fr之其中一种。
4、如权利要求3所述的匹配锂离子二次电池天然石墨负极的电解液,其特征在于,所述含硼元素化合物BF3或B2O3。
5、如权利要求4所述的匹配锂离子二次电池天然石墨负极的电解液,其特征在于,所述的含硼元素化合物占总重量的0.1%~10%。
6、如权利要求5所述的匹配锂离子二次电池天然石墨负极的电解液,其特征在于,所述的有机溶剂成份及各成份的质量比为:EC/EMC/DMC/DEC/PC=3/2/2/2/1;电解质锂盐为LiPF6,浓度为1.1M。
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CN102456916A (zh) * | 2010-10-29 | 2012-05-16 | 株式会社日立制作所 | 锂离子二次电池 |
CN105655638A (zh) * | 2014-11-14 | 2016-06-08 | 宁德时代新能源科技股份有限公司 | 锂金属电池及其电解液 |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102456916A (zh) * | 2010-10-29 | 2012-05-16 | 株式会社日立制作所 | 锂离子二次电池 |
CN105655638A (zh) * | 2014-11-14 | 2016-06-08 | 宁德时代新能源科技股份有限公司 | 锂金属电池及其电解液 |
CN105655638B (zh) * | 2014-11-14 | 2019-12-13 | 宁德时代新能源科技股份有限公司 | 锂金属电池及其电解液 |
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