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VoLTE improves different networks in different ways.
On all networks, it's a lot better at handling voice & data simultaneously so a practical application would be voice calls continuing while you use Google Maps, for example. Calls will also setup in (sometimes) under a second compared with legacy technologies. And the networks can hold a LOT more voice calls per unit of 4G spectrum compared with 3G.
On EE & 3, VoLTE also unlocks access to Band20 coverage which, as others have pointed out, improves rural and indoor coverage noticeably. O2 & VF's original 2G & 3G networks were built on 900Mhz, so don't have this issue.
Historically, O2 & VF haven't had VoLTE in all areas whereas EE have. In other words, you could have 4G coverage on O2 but still fallback to 2G/3G for voice calls - EE have always had a blanket-VoLTE setup. The other thing is that VoLTE & VoWiFi use the same core network, so a 4G voice call can seamless handover to a WiFi voice call (where the facility exists) and vice-versa without the call dropping.
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